Synthesis of α- and β-C-Aryl Δ2-Glycopyranosides from p-tert-Butylphenyl Δ2-Glycopyranosides via Grignard Reagents

Article abstract of DOI:10.1021/jo9714674

Treatment of p-tert-butylphenyl 4,6-di-O-benzyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside (1aα) or the 4,6-di-O-(tert-butyldimethylsilyl) analogue (1bα) with various functionalized arylmagnesium bromides in the presence of a catalytic amount of PdCl₂(dppf) at 25°C in THF afforded the corresponding unsaturated C-arylglycosides 2-14 having the α-configuration in quite good yields. Benzyl-, allyl-, and vinylmagnesium bromides gave also the corresponding unsaturated α-C-glycosides 15-18, although in lower yields. When the same reaction was performed in the presence of NiCl₂(dppe) as the catalyst at -40°C, only the formation of the corresponding unsaturated C-arylglycosides having the β-configuration was observed. As expected, reaction of phenylmagnesium bromide with p-tert-butylphenyl 4,6-di-O-benzyl-2,3-dideoxy-β-D-erythro-hex-2-enopyranoside (1aβ) in the presence of NiCl₂(dppe) gave only the unsaturated β-C-phenylglycoside 2aβ, while palladium-catalyzed reaction led to the preponderant formation of C-phenylglycoside 2aα. Reaction of PhMgBr with p-tert-butylphenyl 4-O-benzyl-2,3,6-trideoxy-α-L-erythro-hex-2-enopyranoside (20) afforded stereospecifically the unsaturated α- and β-C-phenylglycoside 25 in the presence of PdCl₂-(dppf) and NiCl₂(dppe), respectively.

Full text of DOI:10.1021/jo9714674

582
J . Org. Chem. 1998, 63, 582-591
Syn th esis of r- a n d â-C-Ar yl ∆2-Glycop yr a n osid es fr om
p-ter t-Bu tylp h en yl ∆2-Glycop yr a n osid es via Gr ign a r d Rea gen ts
Christophe Moineau, Ve´ronique Bolitt, and Denis Sinou*
Laboratoire de Synthe`se Asyme´trique, associe´ au CNRS, CPE Lyon, Universite´ Claude Bernard Lyon I,
43 Boulevard du 11 Novembre 1918, 69622 Villeurbanne Ce´dex, France
Received August 6, 1997
Treatment of p-tert-butylphenyl 4,6-di-O-benzyl-2,3-dideoxy-R-D-erythro-hex-2-enopyranoside (1a r)
or the 4,6-di-O-(tert-butyldimethylsilyl) analogue (1br) with various functionalized arylmagnesium
bromides in the presence of a catalytic amount of PdCl2(dppf) at 25 °C in THF afforded the
corresponding unsaturated C-arylglycosides 2-14 having the R-configuration in quite good yields.
Benzyl-, allyl-, and vinylmagnesium bromides gave also the corresponding unsaturated R-C-
glycosides 15-18, although in lower yields. When the same reaction was performed in the presence
of NiCl2(dppe) as the catalyst at -40 °C, only the formation of the corresponding unsaturated
C-arylglycosides having the â-configuration was observed. As expected, reaction of phenylmag-
nesium bromide with p-tert-butylphenyl 4,6-di-O-benzyl-2,3-dideoxy-â-D-erythro-hex-2-enopyranoside
(1a â) in the presence of NiCl2(dppe) gave only the unsaturated â-C-phenylglycoside 2a â, while
palladium-catalyzed reaction led to the preponderant formation of C-phenylglycoside 2a r. Reaction
of PhMgBr with p-tert-butylphenyl 4-O-benzyl-2,3,6-trideoxy-R-L-erythro-hex-2-enopyranoside (20)
afforded stereospecifically the unsaturated R- and â-C-phenylglycoside 25 in the presence of PdCl2-
(dppf) and NiCl2(dppe), respectively.
C-Arylglycosides have attracted considerable synthetic
As part of our interest in the field of organometallic-
catalyzed functionalization at the anomeric center of
carbohydrates,6 we recently described the stereospecific
palladium- and nickel-catalyzed access to unsaturated R-
and â-C-arylglycopyranosides.7 In this paper, we give a
full account of the formation of these C-arylglycopyra-
nosides.
work during the past decade,1 because of the antibiotic
and/or antiviral activities of many products containing
this structural unit. Such derivatives also constitute
attractive intermediates for the construction of more
complex and exciting targets. In particular, C-arylgly-
copyranosides with a double bond in the 2,3-position are
versatile synthons, since this unsaturation can further
be functionalized by epoxidation, hydroxylation, or hy-
droboration for the synthesis of natural products. The
usual synthetic approaches to such unsaturated com-
pounds involved palladium(II)-mediated arylation of gly-
cals,2 palladium(0)-catalyzed addition of arylzinc deriva-
tives to hex-2-enopyranosides,3 Lewis acid promoted
reaction of phenols with glycals,4 or addition of halo-
genomagnesium phenates to these glycals.5 Although the
chemical yields of these different methodologies are
generally high, they actually suffer either from lack of
selectivity or from the formation of one anomer only, the
R derivative being generally preponderant.
Resu lts a n d Discu ssion
Transition-metal catalyzed substitution of allylic sub-
strates with organometallic reagents is an important and
well-documented carbon-carbon bond-forming reaction
in organic synthesis.8 These organometallic reagents
mainly based on aluminum,9 boron,10 magnesium,11 tin,12
(6) (a) Brakta, M.; Lhoste, P.; Sinou, D. J . Org. Chem. 1989, 54,
1890. (b) Chaguir, B.; Brakta, M.; Bolitt, V.; Lhoste, P.; Sinou, D. J .
Carbohydr. Chem. 1992, 11, 609. (c) Bolitt, V.; Chaguir, B.; Sinou, D.
Tetrahedron Lett. 1992, 33, 2481.
(7) Moineau, C.; Bolitt, V.; Sinou, D. Chem. Commun. 1995, 1103.
(8) Reviews: (a) Tamao, K. In Comprehensive Organic Synthesis;
Trost, B. M., Fleming, I., Pattenden, G., Eds.; Pergamon: Oxford, 1991;
(1) Reviews: (a) Hacksell, U.; Daves, G. D. Prog. Med. Chem. 1985,
22, 1. (b) J aramillo, C.; Knapp, S. Synthesis 1993, 1. (c) Postema M.
H. D. Tetrahedron 1992, 48, 8545. (d) Postema, M. H. D. C-Glycoside
Synthesis; CRC Press: London, 1995; pp 119 and 265.
(2) (a) Kwok, D.-I.; Farr, R. N.; Daves, G. D., J r. J . Org. Chem. 1991,
56, 3711. (b) Czernecki, S.; Dechavanne, V. Can. J . Chem. 1983, 61,
533. (c) Bellosta, V.; Czernecki, S.; Avenel, D.; El Bahij, S.; Gillier-
Pandraud, H. Can. J . Chem. 1990, 68, 1364. (d) Daves, G. D., J r. Acc.
Chem. Res 1990, 23, 201. (e) Daves, G. D., J r.; Hallberg, A. Chem. Rev.
(Washington, D.C.) 1989, 89, 1433.
(3) (a) Dunkerton, L. V.; Serino, A. J . J . Org. Chem. 1982, 47, 2812.
(b) Dunkerton, L. V.; Euske, J . M.; Serino, A. J . Carbohydr. Res. 1987,
171, 89.
(4) Ramesh, N. G.; Balasubramanian, K. K. Tetrahedron Lett. 1992,
33, 3061.
(5) (a) Casiraghi, G.; Cornia, M.; Rassu, G.; Zetta, L.; Fava, G. G.;
Belicchi, M. F. Tetrahedron Lett. 1988, 29, 3323. (b) Casiraghi, G.;
Cornia, M.; Colombo, L.; Rassu, G.; Fava, G. G.; Belicchi, M. F.; Zetta,
L. Tetrahedron Lett. 1988, 29, 5549. (c) Casiraghi, G.; Cornia, M.;
Rassu, G.; Zetta, L.; Fava, G. G.; Belicchi, M. F. Carbohydr. Res. 1989,
191, 243.
Vol. 3,
p 435. (b) Consiglio, G.; Waymouth, R. M. Chem. Rev.
(Washington, D.C.) 1989, 89, 257. (c) Miyaura, N.; Suzuki, A. Chem.
Rev. (Washington, D.C.) 1995, 95, 2457.
(9) (a) Matsushita, H.; Negishi, E. J . Am. Chem. Soc. 1981, 103,
2882. (b) Negishi, E.; Chatterjee, S.; Matsushita, H. Tetrahedron Lett.
1981, 22, 3737. (c) Matsushita, H.; Negishi, E. Chem. Commun. 1982,
160. (d) Hutzinger, M. W.; Oehlschlager, A. C. J . Org. Chem. 1991,
56, 2918.
(10) (a) Miyaura, N.; Yano, T.; Suzuki, A. Tetrahedron Lett. 1980,
21, 2865. (b) Miyaura, N.; Tanabe, Y.; Suginome, H.; Suzuki, A. J .
Organomet. Chem. 1982, 233, C13. (c) Kurosawa, H.; Ogoshi, S.;
Kawasaki, Y.; Murai, S.; Miyoshi, M.; Ikeda, I. J . Am. Chem. Soc. 1990,
112, 2813. (d) Legros, J .-Y.; Fiaud, J .-C. Tetrahedron Lett. 1990, 31,
7453. (e) Kobayashi, Y.; Ikeda, E. Chem. Commun. 1994, 1789. (f)
Mizojiri, R.; Kobayashi, Y. J . Chem. Soc., Perkin Trans. 1 1995, 2073.
(g) Trost, B. M.; Spagnol, M. D. J . Chem. Soc., Perkin Trans. 1 1995,
2083. (i) Kobayashi, Y.; Mizojiri, R.; Ikeda, E. Synlett 1995, 571. (j)
Kobayashi, Y.; Mizojiri, R.; Ikeda, E. J . Org. Chem. 1996, 61, 5391.
(k) Kobayashi, Y.; Watatani, K.; Kikori, Y.; Mizojiri, R. Tetrahedron
Lett. 1996, 37, 6125.
S0022-3263(97)01467-9 CCC: $15.00 © 1998 American Chemical Society
Published on Web 01/14/1998

Synthesis of R- and â-C-Aryl ∆2-Glycopyranosides
J . Org. Chem., Vol. 63, No. 3, 1998 583
zinc,13 and zirconium14 are known to couple under very
mild conditions in the presence of palladium and/or nickel
catalysts with net inversion of configuration. We ex-
pected that reaction of an appropriate organometallic
reagent with p-tert-butylphenyl 4,6-di-O-benzyl-2,3-
dideoxy-R-D-erythro-hex-2-enopyranoside (1a )15 in the
presence of a palladium or nickel catalyst would give
regio- and stereoselectively the unsaturated C-arylgly-
copyranoside.
In itia l Stu d ies. Thus, we initiated a study to deter-
mine which organometallic reagent/catalyst system will
allow the stereospecific introduction of a phenyl moiety
at the anomeric center of unsaturated carbohydrate 1a r.
From the literature data we selected NaBPh4, PhSnBu3,
PhZnCl, and PhMgBr as the organometallic reagent and
various palladium and nickel complexes as the catalysts.
The reactions were explored with unsaturated sugar 1a .
Preliminary experiments show that NaBPh4 in the pres-
ence of Pd(dba)2 + 4 PPh3 or PhSnBu3 in the presence of
various catalysts such as Pd2(dba)3, Pd2(dba)3 + LiCl, Pd2-
(dba)3 + 2 dppb [dppb ) 1,4-bis(diphenylphosphino)-
butane], PdCl2(PPh3)2, or PdCl2(dppf) [dppf ) 1,1′-bis-
(diphenylphosphino)ferrocene] gave no reaction. The use
Ta ble 1. Ca ta lyst Effect in P a lla d iu m a n d Nick el
Ca ta lyzed Cou p lin g of C6H5MgBr a n d 1Ara
organo-
entry metallic
temp time
product
catalyst
(°C)
(h)
(yield %)b
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
PhMgBr Pd2(dba)3 + 4PPh3
PhMgBr PdCl2(PPh3)2
PhMgBr PdCl2[P(o-tolyl)3]2
PhMgBr PdCl2[P(2-furyl)3]2
PhMgBr PdCl2(dppf)
PhMgBr PdCl2(dppe)
PhMgBr PdCl2(dppp)
PhMgBr PdCl2(dppb)
PhMgBr PdCl2(dpppe)
PhMgBr NiCl2(dppe)
PhMgBr NiCl2(dppp)
PhMgBr NiCl2(dppb)
PhMgBr NiCl2(dppb)
PhMgBr NiCl2(dpppe)
PhMgBr NiCl2(dpppe)
PhMgBr NiCl2(PPh3)2
PhMgBr NiCl2(PPh3)2
25
25
25
25
25
25
25
25
25
-40
-20
-20
0
24
20
20
20
2
20
20
20
20
2
48
24
24
24
24
24
24
degradation
no reaction
no reaction
no reaction
2a r (95)
2a r (10)
2a r (40)
2a r (14)
no reaction
2a â (70)
2a â (64)
no reaction
degradation
no reaction
degradation
no reaction
degradation
-20
0
-20
0
a
Reactions were carried out with 5 equiv of organometallic
reagent in the presence of 10 mol % of the catalyst in THF.
Isolated yield of analytical pure material.
b
of PhZnCl in the presence of Pd2(dba)3 + 4 PPh3, PdCl2-
(PPh3)2, or PdCl2(dppf) as the catalyst gave also no
reaction or only degradation products. However, when
PhMgBr (5 equiv) was used as the organometallic reagent
in the presence of 10 mol % of a palladium complex, in
THF at 25 °C, the yield of unsaturated C-aryl carbohy-
drate appears to be ligand dependent (Table 1). Forma-
tion of C-phenylglycoside 2a r occurred in 95% yield using
PdCl2(dppf) as the catalyst (Table 1, entry 5). PdCl2-
(dppp) [dppp ) 1,3-bis(diphenylphosphino)propane] as
catalyst gave compound 2a r in 40% yield (Table 1, entry
7), all other combinations of palladium with bidentate
ligands such as dppe [dppe ) 1,2-bis(diphenylphosphino)-
ethane)], dppb, or dpppe [dpppe ) 1,5-bis(diphenylphos-
phino)pentane] gave very low yields of coupling product
or no reaction at all (Table 1, entries 6, 8, and 9). The
palladium complex PdCl2L2, where L is a monodentate
phosphine, gave no reaction (Table 1, entries 2-4),
although the combination of Pd2(dba)3 and 4PPh3 gave
degradation products (Table 1, entry 1). It is to be
noticed that the preformed catalyst PdCl2L2 or the system
obtained by mixing PdCl2(CH3CN)2 and 2 equiv of a
monophosphine or 1 equiv of a diphosphine in situ gave
the same results.
(11) (a) Chuit, C.; Felkin, H.; Frajerman, C.; Roussi, G.; Swiercze-
wski, G. Chem. Commun. 1968, 1604. (b) Heck, R. F. J . Am. Chem.
Soc. 1968, 90, 5531. (c) Felkin, H.; Swierczewski, G. Tetrahedron Lett.
1972, 1433. (d) Felkin, H.; Swierczewski, G. Tetrahedron 1975, 31,
2735. (e) Felkin, H.; J ampel-Costa, E.; Swierczewski, G. J . Organomet.
Chem. 1977, 134, 265. (f) Chuit, C.; Felkin, H.; Frajerman, C.; Roussi,
G.; Swierczewski, G. J . Organomet. Chem. 1977, 127, 371. (g) Buck-
walter, B. L.; Burfitt, I. R.; Felkin, H.; J oly-Goudket, M.; Naemura,
K.; Salomon, M. F.; Wenkert, E.; Wovkulich, P. M. J . Am. Chem. Soc.
1978, 100, 6445. (h) Larock, R. C.; Bernhardt, J . C.; Driggs, R. J . J .
Organomet. Chem. 1978, 156, 45. (i) Castanet, Y.; Petit, F. Tetrahedron
Lett. 1979, 3221. (j) Okamura, H.; Takei, H. Tetrahedron Lett. 1979,
3425. (k) Consiglio, G.; Morandini, F.; Piccolo, O. J . Am. Chem. Soc.
1981, 103, 1846. (l) Felkin, H.; J oly-Goudket, M.; Davis, S. G.
Tetrahedron Lett. 1981, 22, 1157. (m) Negishi, E.; Chatterjee, S.;
Matsushita, H. Tetrahedron Lett. 1981, 22, 3737. (n) Hayashi, T.;
Konishi, M.; Kumada, M. Chem. Commun. 1984, 107. (o) Goliaszewski,
A.; Schwartz, J . J . Am. Chem. Soc. 1984, 106, 5028. (p) Urabe, H.;
Inami, H.; Sato, F. Chem. Commun. 1993, 1595. (q) Hayashi, T.;
Konishi, M.; Yokota, K.; Kumada, M. J . Organomet. Chem. 1985, 285,
359. (r) Kobayashi, Y.; Ikeda, E. Chem. Commun. 1994, 1789. (s)
Didiuk, M. F.; Morken, J . P.; Hoveyda, A. H. J . Am. Chem. Soc. 1995,
117, 7273. (t) Lautens, M.; Ma, S. J . Org. Chem. 1996, 61, 7246. (u)
Sugimura, H.; Takei, H. Chem. Lett. 1985, 351. (v) Hiyama, T.; Wakasa,
N. Tetrahedron Lett. 1985, 26, 3259. (w) Consiglio, G.; Piccolo, O.;
Roncetti, L. Tetrahedron 1986, 42, 2043. (x) Yanagisawa, A.; Nomura,
N.; Yamamoto, H. Tetrahedron 1994, 50, 6017.
(12) (a) Sheffy, F. K.; Stille, J . K. J . Am. Chem. Soc. 1983, 105, 7173.
(b) Sheffy, F. K.; Goldschalx, J . P.; Stille, J . K. J . Am. Chem. Soc. 1984,
106, 4833. (c) Kosugi, M.; Ohashi, K.; Akuzawa, K.; Kawazoe, T.; Sano,
H.; Migita, T. Chem. Lett. 1987, 1237. (d) Tueting, D. R.; Echavarren,
A. M.; Stille, J . K. J . Am. Chem. Soc. 1988, 110, 4039. (e) Farina, V.;
Baker, S. R.; Begnini, D. A.; Sapino, C., J r. Tetrahedron Lett. 1988,
29, 5739. (f) Tolstikov, G. A.; Miftakhov, M. S.; Danilova, N. A.; Vel’der,
Y. L.; Spirikhin, L. V. Synthesis 1989, 625. (g) Tueting, D. R.;
Echavarren, A. M.; Stille, J . K. Tetrahedron 1989, 45, 979. (h)
Kurosawa, H.; Ogoshi, S.; Kawasaki, Y.; Murai, S.; Miyoshi, M.; Ikeda,
I. J . Am. Chem. Soc. 1990, 112, 2813. (i) Del Valle, L.; Stille, J . K.;
Hegedus, L. S. J . Org. Chem. 1990, 55, 3019. (j) Farina, V.; Baker, S.
R.; Begnini, D. A.; Hauck, S. I.; Sapino, C., J r. J . Org. Chem. 1990,
55, 5833. (k) Knight, S.; Overman, L. E.; Pairaudeau, G. J . Am. Chem.
Soc. 1995, 117, 5776. (l) Castan˜o, A. M.; Echavarren, A. M. Tetrahedron
Lett. 1996, 37, 6587.
The coupling reaction of PhMgBr with unsaturated
carbohydrate 1a r in THF catalyzed by 10 mol % nickel
complexes is also ligand dependent. When NiCl2(dppe)
or NiCl2(dppp) were used as the catalyst (Table 1, entries
10 and 11), the C-arylglycoside 2a â was obtained in 70%
and 64% yield, respectively. The other catalysts NiCl2-
(dppb), NiCl2(dppe), and NiCl2(PPh3)2 gave degradation
products at 0 °C or no reaction at -20 °C (Table 1, entries
12-17).
The R- and â-configurations of compounds 2a were
determined on the basis of 1H and 13C nuclear magnetic
resonance,6a,16 some pertinent data concerning pairs of
anomers being summarized in Table 2. As shown before,
the â-anomer is conformationally stable in the 0H5
conformation, whereas the R-anomer exists as an equili-
(13) (a) Negishi, E.; Chatterjee, S.; Matsushita, H. Tetrahedron Lett.
1981, 22, 3737. (b) Keinan, E.; Sahai, M. Chem. Commun. 1984, 648.
(c) Dunkerton, L. V.; Serino, A. J . J . Org. Chem. 1982, 47, 2812. (d)
Fiaud, J .-C.; Aribi-Zouioueche, L. J . Organomet. Chem. 1985, 295, 383.
(e) Hayashi, T.; Yamamoto, A.; Hagihara, T. J . Org. Chem. 1986, 51,
723. (f) Fiaud, J .-C.; Legros, J .-Y. J . Org. Chem. 1987, 52, 1907. (g)
Agrios, K. A.; Srebnik, M. J . Org. Chem. 1994, 59, 5468.
(14) (a) Hayashi, Y.; Riediker, M.; Temple, J . S.; Schwartz, J .
Tetrahedron Lett. 1981, 22, 2629. (b) Negishi, E.; Chatterjee, S.;
Matsushita, H. Tetrahedron Lett. 1981, 22, 3737. (c) Temple, J . S.;
Riediker, M.; Schwartz, J . J . Am. Chem. Soc. 1982, 104, 1310. (d)
Hutzinger, M. W.; Oehlschlager, A. C. J . Org. Chem. 1991, 56, 2918.
(15) Frappa, I.; Sinou, D. Synth. Commun. 1995, 25, 2941.
0
5
brating mixture of the H5 and H0 conformations. Thus,
(16) Brakta, M.; Farr, R. N.; Chaguir, B.; Massiot, G.; Lavaud, C.;
Anderson, W. R., J r.; Sinou, D.; Daves, G. D., J r. J . Org. Chem. 1993,
58, 2992.

584 J . Org. Chem., Vol. 63, No. 3, 1998
Moineau et al.
Ta ble 2. Sp ectr a l Da ta P er tin en t to Ster eoch em ica l
Ta ble 3. P a lla d iu m -Ca ta lyzed Cou p lin g Rea ction of 1r
Assign m en ts of th e P a ir s of r- a n d â-C-Ar ylglycosid esa
a n d Va r iou s Gr ign a r d Rea gen tsa
b
c
compd
[R]20
δ H-1′
J 4′,5′
δ C-1′
δ C-5′
temp time
product
D
entry 1r
RMgBr
C6H5MgBr
C6H5MgBr
4-MeC6H4MgBr
4-MeC6H4MgBr
2-MeC6H4MgBr
4-MeOC6H4MgBr
3-MeOC6H4MgBr
2-MeOC6H4MgBr
3,4-(CH2O2)C6H3MgBr
4-ClC6H4MgBr
(°C)
(h)
(yield, %)b
2a r
2a â
2br
2bâ
3a r
3a â
3bâ
3bâ
5a r
5a â
6a r
6a â
7a r
7a â
8a r
8a â
10a r
10a â
25rd
25âd
+18.5
+60.8
+3.9
5.30
5.18
5.28
5.16
5.30
5.15
5.23
5.13
5.26
5.14
5.28
5.17
5.69
5.61
5.20
5.12
5.27
5.12
5.21
5.14
7.3
8.6
8.1
8.5
7.0
8.4
8.0
8.5
7.5
8.7
7.9
8.7
7.4
8.5
7.1
8.3
7.2
8.2
74.1
77.8
74.6
77.3
74.0
78.0
74.4
77.2
73.9
77.3
74.2
77.9
71.5
71.6
73.9
77.9
73.9
78.1
75.8
77.8
70.1
77.4
73.7
80.7
70.5
77.4
73.6
80.8
70.3
78.1
71.1
77.4
70.3
78.0
70.4
77.3
70.4
77.3
67.9
76.7
1
2
a
b
a
b
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
0
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
1
2
2
4
2
2
2a r (95)
2br (80)
+189.1
-2.6
3
4
5
6
3a r (70)
3br (70)
+171.0
-3.1
4a r (80)
5a r (73)
+145.5
-3.8
7
8
9
6a r (60)
7a r (87)
+175.8
+9.1
8a r (95)
10
11
12
13
14
15
16
17
18
19
20
21
9a r (76)
+169.0
+15.5
+151.0
+11.7
+162.5
-9.2
4-ButMe2SiOC6H4MgBr
4-[(MeO)2CH]C6H4MgBr
4-C2H3C6H4MgBr
2-MgBr-thiophene
2-MgBr-naphthalene
2-MgBr-naphthalene
PhCH2MgBr
CH2dCHCH2MgBr
CH2dCHCH2MgBr
CH2dCHMgBr
10a r (65)
11a r (65)
13a r (72)
14a r (81)
degradation
15a r (78)
16a r (70)
degradation
17a r (72)
degradation
18a r (14)
+123.8
-20.6
-219.2
25
25
-10
25
0
8.4
δ in ppm; J in hertz. In CH2Cl2. c brs. L series.
a
b
d
CH2dCHMgBr
a
the higher coupling constant would be attributed to the
â-anomer; we effectively observed J 4′,5′ ) 8.6 Hz for 2â
and J 4′,5′ ) 7.3 Hz for 2r.
Reactions were carried out with 5 equiv of the Grignard
reagent in the presence of 10 mol % of PdCl2(dppf) in THF.
b Isolated yields of analytically pure material. c Catalyst PdCl2(dppp).
This assignment was confirmed by 13C NMR. Due to
the γ-gauche effect described by Stothers17 and also
recently observed for unsaturated C-glycopyranosyl com-
pounds,16 derivative 2r shows a C-5′ signal at a higher
field (δ 70.1 ppm) than compound 2â (δ 77.4 ppm). An
upfield shift of the C-1′ in 2r (δ 74.1 ppm) was also
observed compared to the downfield shift for 2â (δ 77.8
ppm).
NOE experiments were also used to confirm the
configuration at the anomeric center. Irradiation of the
C-1′ methine proton (δ 5.18 ppm) in compound 2â
obtained via nickel catalysis shows an enhancement of
10% of the C-5′ methine proton signal at δ 3.75 ppm, in
agreement with a syn disposition of these two atoms. A
similar experiment on compound 2a r obtained via pal-
ladium catalysis shows no enhancement.
Cou p lin g Rea ction Ca ta lyzed by P a lla d iu m Com -
p lexes. To survey the coupling reaction catalyzed by
PdCl2(dppf), various Grignard reagents and unsaturated
carbohydrates 1a -br were subjected to this reaction in
THF. The results are shown in Table 3.
Reactions of (4- and 2-methylphenyl)magnesium bro-
mides as well as (4-, 3-, and 2-methoxyphenyl)magnesium
bromides with 1a r gave high yields of the corresponding
R-C-arylglycosides 3a -7a r (Table 3, entries 3 and 5-8).
Using p-tert-butylphenyl 4,6-di-O-(tert-butyldimethylsi-
lyl)-2,3-dideoxy-R-D-erythro-hex-2-enopyranoside (1b) in-
stead of 1a also gave quite good yields of the R-anomer
with phenyl- or (4-methylphenyl)magnesium bromide
(Table 3, entries 2 and 4).
(4-Vinylphenyl)- and thiopheneylmagnesium bromides
also coupled with carbohydrate 1a r to give the interest-
ing R-C-styryl and C-thiopheneyl carbohydrates 13 and
14, respectively (Table 3, entries 13 and 14). The
Grignard reagent of 2-bromonaphthalene led to the
expected coupling product 15ra in 78% yield, but only
at 0 °C; performing the reaction at 25 °C gave degrada-
tion products (Table 3, entries 15 and 16).
We extended the reaction to nonaromatic Grignard
reagents. Thus, benzyl- and allylmagnesium bromides
reacted with 1a r to give the R-C-benzyl and allyl
compounds 16 and 17 in 70 and 72% yield, respectively,
although the reaction has to be performed at -10 °C in
the last case (Table 3, entries 17-19). The R-configura-
tion at C-1′ was confirmed for compound 17 by NOE
experiments. Irradiation of the benzylic protons at δ 2.82
and 3.08 ppm effectively shows an enhancement of 7%
of the signal of H-5′ at δ 3.91 ppm. Vinylmagnesium
bromide formed 18r in 14% yield at 0 °C (Table 3, entries
20-21), whereas (phenylacetylenyl)magnesium bromide
gave no reaction.
Methylmagnesium bromide did not give the expected
coupling product, the C-glycoside 19r being obtained in
52% yield (Scheme 2). Such a O f C transformation was
used before by Casiraghi et al.5 for the preparation of
C-arylglycosides.
Cou p lin g Rea ction Ca ta lyzed by Nick el Com -
p lexes. Various Grignard reagents were also reacted
with unsaturated substrates 1a -br in THF in the
presence of 10% NiCl2(dppe) as the catalyst. The results
are summarized in Table 4.
Grignard reagents derived from 1-bromo-3,4-dioxom-
ethylbenzene and 1-bromo-4-chlorobenzene, as well as
from 1-bromo-4-[(tert-butyldimethylsilyl)oxy]benzene and
4-bromobenzaldehyde dimethyl acetal, reacted under
these conditions to give respectively the corresponding
R-C-glycosides 8a , 9a , 10a , and 11a in quite good yields
(Table 3, entries 9-12).
Reaction of phenyl- and (4-methylphenyl)magnesium
bromides with 1a r or 1br at -40 °C gave the expected
unsaturated phenylglycosides 2â and 3â in quite good
yields (Table 4, entries 1-3 and 6). It is to be noticed
that the use of NiCl2(dppf) as the catalyst gave no
reaction at -40 °C and only 12% yield at 0 °C (Table 4,
entries 4-5).
(17) (a) Stothers, J . B. Carbon-13 NMR Spectroscopy; Academic
Press: New York, 1973; Chapter 3. (b) Kalinowski, H. O.; Berger, S.;
Braun, S. Carbon-13 NMR Spectroscopy; Academic Press: New York,
1988; Chapter 3.
While (4- and 3-methoxyphenyl)magnesium bromides
reacted at -40 °C to give 5a â and 6a â in 75 and 60%

Synthesis of R- and â-C-Aryl ∆2-Glycopyranosides
J . Org. Chem., Vol. 63, No. 3, 1998 585
Sch em e 1
observed in the case of palladium-catalyzed reaction and
the â-anomer in the case of nickel-catalyzed reaction.
However, in the case of nickel catalysts, the temperature
seems very important for the success of the coupling.
Cou p lin g Rea ction of P h en ylm a gn esiu m Br o-
m id e w ith Oth er Ca r boh yd r a tes. In the above sec-
tions, we described the palladium and the nickel coupling
of various arylmagnesium bromides and p-tert-butylphe-
nyl 4,6-di-O-benzyl-2,3-dideoxy-R-D-erythro-hex-2-enopy-
ranoside (1a ). To gain a deeper insight into the poten-
tialities of this transformation in carbohydrate chemistry,
we applied these experimental conditions to other car-
bohydrates.
p-tert-Butylphenyl 4-O-benzyl-2,3,6-trideoxy-R-L-erythro-
hex-2-eno pyranoside (20) was prepared according to the
literature.15 The synthesis of p-tert-butylphenyl 4,6-di-
O-benzyl-2,3-dideoxy-â-D-erythro-hex-2-enopyranoside
(1a â) is described in Scheme 3. The mother liquor
obtained after recrystallization during the preparation
of 1a r16 was subjected to deacetylation. The mixture was
then treated with 1 equiv of TBDMSCl in CH2Cl2 in the
presence of imidazole to give the monosilylated com-
pounds 21r and 21â. Separation of both anomers by
column chromatography gave pure 21â in 30% yield.
Subsequent desilylation of 21â using Bu4NF‚3H2O in
THF followed by benzylation with benzyl bromide in the
presence of Bu4NBr and sodium hydroxide led to 1a â in
91% yield.
Sch em e 2
Ta ble 4. Nick el-Ca ta lyzed Cou p lin g Rea ction of 1r a n d
Va r iou s Gr ign a r d Rea gen tsa
The 2,3-unsaturated threo derivatives 23 and 24c were
prepared according to Scheme 4. Inversion of configu-
ration at C-4 of 21r via a Mitsunobu reaction18 gave the
threo derivative 22. Desilylation of 22 followed by
alkylation of the resulting diol with benzyl bromide led
to the 4,6-di-O-benzyl-2,3-unsaturated threo derivative
23. Treatment of alcohol 22 with NaH and methyl iodide
in THF led to the O-methyl carbohydrate 24a . Subse-
quent desilylation of 24a followed by benzylation under
the conditions already described formed the unsaturated
compound 24c.
Reaction of phenylmagnesium bromide with the un-
saturated carbohydrate 20 in the presence of a catalytic
amount of PdCl2(dppf) (Scheme 5) gave glycoside 25r in
51% yield, whereas the nickel-catalyzed reaction gave 25â
in 68% yield. Thus, we found the same stereoselectivities
as with the unsaturated carbohydrates 1a -b.
Arylation of 1a â under the same conditions gave
phenylglycoside 2a in 87% yield as a mixture of anomers
R/â ) 95/5, in the case of the palladium-catalyzed
reaction, and only the â-anomer in 50% yield for the
nickel-catalyzed reaction (Scheme 6). These results
excluded the possibility of an ionic intermediate in the
arylation reaction.
Finally, this arylation process was extended to the
threo derivatives 23 and 24c. In the case of the di-O-
benzyl derivative 23, no reaction was observed using
PdCl2(dppf) at 0-50 °C or NiCl2(dppe) at -20 °C as the
catalysts, although performing the reaction at 0 °C in the
latter case gave degradation products. However, in the
arylation of the methoxy derivative 24c, while the nickel
catalysis gave no reaction or degradation products, the
palladium-catalyzed reaction led to the formation of
C-phenylglycoside 26r in 44% yield. The difference of
reactivity between 23 and 24c could be attributed to the
temp time
product
entry 1r
RMgBr
C6H5MgBr
(°C)
(h)
(yield, %)b
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
a
b
a
a
a
b
a
a
a
a
a
b
a
b
b
a
a
-40
-40
-40
-40
0
-40
-40
-40
-40
-20
-40
+10
2
2
2
2
15
2
2
2
24
2
2
2
2
20
2
2
2a â (70)
C6H5MgBr
2bâ (83)
4-MeC6H4MgBr
4-MeC6H4MgBrc
4-MeC6H4MgBrc
4-MeC6H4MgBr
4-MeOC6H4MgBr
3-MeOC6H4MgBr
2-MeOC6H4MgBr
2-MeOC6H4MgBr
3,4-(CH2O2)C6H3MgBr
4-ClC6H4MgBr
3a â (85)
no reaction
3a â (12)
3bâ (83)
5a â (75)
6a â (60)
no reaction
7a â (64)
8a â (70)
9bâ (60)
10a â (90)
10bâ (81)
12bâ (80)
no reaction
degradation
4-ButMe2SiOC6H4MgBr -40
4-ButMe2SiOC6H4MgBr -40
4-MOMOC6H4MgBr
2-MgBr-thiophene
2-MgBr-thiophene
-40
-20
0
2
a
Reactions were carried out with 5 equiv of the Grignard
reagent in the presence of 10 mol % of NiCl2(dppe) in THF.
b Isolated yields of analytically pure material. c Catalyst NiCl2(dppf).
yield, respectively (Table 4, entries 7 and 8), (2-methox-
yphenyl)magnesium bromide reacted at -20 °C to pro-
duce the expected 7a â in 64% yield (Table 4, entries 9
and 10).
Grignard reagents derived from 1-bromo-3,4-dioxom-
ethylbenzene, 1-bromo-4-[(tert-butyldimethylsilyl)oxy]-
benzene, and 1-bromo-4-(methoxymethoxy)benzene readily
reacted at -40 °C to give the unsaturated carbohydrates
8a â, 10â and 12bâ in quite good yields (Table 4, entries
11 and 13-15). (4-Chlorophenyl)magnesium bromide
reacted only at 10 °C, giving 9bâ in 60% yield (Table 4,
entry 12), although thiopheneylmagnesium bromide gave
no alkylated compound whatever the conditions (Table
4, entries 16 and 17).
So, in all examined cases leading to the formation of
unsaturated C-aryl carbohydrates, the reaction was
totally stereoselective, with only the R-anomer being
(18) Sa¨ıah, M.; Bessodes, M.; Antonakis, K. Tetrahedron Lett. 1992,
33, 4317.

586 J . Org. Chem., Vol. 63, No. 3, 1998
Moineau et al.
Sch em e 3a
a
(a) CH3OH, CH3ONa; (b) TBDMSCl, NEt3, imidazole, CH2Cl2, 25 °C; (c) separation; (d) Bu4NF‚3H2O, THF, 25 °C; (e) BnCl, Bu4NBr,
NaOH 50%.
Sch em e 4a
a
(a) ClCH2COOH, PPh3, DEAD, toluol, the CH3ONa, CH3OH; (b) Bu4NF‚3H2O, THF, 25 °C; (c) BnCl, Bu4NBr, NaOH 50%; (d) NaH,
CH3I, THF, 25 °C.
Sch em e 5
Sch em e 7
Sch em e 6
We also observed that the anomeric proton resonates
at higher frequency for the â-anomer in agreement with
previous results.16
It is to be noticed that for a given pair of unsaturated
R- and â-C-glycosylarenes in the D series, the â-anomer
is the more dextrorotatory, disobeying Hudson’s rule18
of isorotation, but in agreement with previous results
published by other groups.2c,5 This rule also applies for
the anomeric L-rhamnosylbenzene 25r and 25â, the
â-anomer now being the less dextrorotatory.
presence of a benzyloxy group at C-4, which overcrowded
the upper face of the double bond, so inhibiting the
formation of the π-allyl intermediate.
However, as previously described,16 these assignments
have to be confirmed by NOE experiments.
Mech a n ism . The stereochemical aspect of the reac-
tion of various organometallic reagents, such as mag-
nesium, boron, aluminum, tin, zinc, or zirconium re-
agents, on π-allyl complexes derived from pal-
ladium9c,11n-q,12a,g,h,13d-f,14c and nickel11j,q-t has been studied
by different groups. In all cases, the reaction proceeded
with overall inversion of configuration, whatever the
metal used.
If the present nickel-catalyzed reaction proceeds with
overall inversion, in agreement with the literature data,
the palladium-catalyzed process shows an overall reten-
tion. It is conceivable that the reaction proceeds as
depicted in Scheme 8. After formation of a Pd(0) or Ni(0)
complex, oxidative addition to the unsaturated carbohy-
drate 1r occurs with inversion of configuration to give a
π-allyl complex. In the case of the allyl-Ni intermediate,
transmetalation with the Grignard reagent leads to a (π-
Str u ctu r a l Assign m en ts. The structures of the
C-arylglycosides, and particularly the R- or â-configura-
tion, were determined on the basis of spectrometric
1
data.16 Pertinent H and 13C nuclear magnetic resonance
data for some pairs of C-arylglycosides are summarized
in Table 2.
As previously shown,16 comparison of J 4′,5′ for R- and
â-anomers show a larger coupling constant for the
â-derivative, although these values cannot be used as the
sole criterion for assignment of the anomeric configura-
tion.
Comparison of the 13C chemical shifts for C-1′ and C-5′
of both anomers show that these atoms for R-C-arylgly-
coside anomers are shielded with respect to the corre-
sponding carbons of â-anomers, the effect being more
pronounced for C-5′ than for C-1′. This is in agreement
with the predictions of the γ-gauche effect.17

Synthesis of R- and â-C-Aryl ∆2-Glycopyranosides
J . Org. Chem., Vol. 63, No. 3, 1998 587
Sch em e 8
butylphenyl 4-O-benzyl-2,3,6-trideoxy-R-L-erythro-hex-2-eno-
allyl)(aryl)-Ni complex which undergoes a syn reductive
elimination to form the unsaturated C-glycosylarene, so
with overall inversion of configuration.
pyranoside (20),15 PdCl2(CH3CN)2, PdCl2(dppf),21 NiCl2-
20
(dppe),22 NiCl2(dppp),23 NiCl2(dppb),22 NiCl2(dpppe),22 NiCl2-
(dppf),24 NiCl2(PPh3)2,22 1-bromo-4-[(tert-butyldimethylsilyl)-
oxy]benzene,25 4-bromobenzaldehyde dimethyl acetal,26 and
1-bromo-4-(methoxymethoxy)benzene.27
In the case of the allyl-Pd intermediate and in light
of the preceding results, the formation of the unsaturated
C-arylglycoside with an overall retention of configuration
is only consistent with an exo attack of the Grignard
reagent on this π-allyl intermediate. However more
experiments are needed to explain in this last case the
mechanistic pathway and to clarify the possible role of
the different oxygen atoms of the molecule.
p-ter t-Bu tylp h en yl 4,6-Di-O-(ter t-bu tyld im eth ylsilyl)-
2,3-d id eoxy-r-D-er yth r o-h ex-2-en op yr a n osid e (1b). A so-
lution of 4.0 g (11 mmol) of p-tert-butylphenyl 4,6-di-O-acetyl-
2,3-dideoxy-R-D-erythro-hex-2-enopyranoside15 in methanol (100
mL) containing 18 mg (0.33 mmol) of CH3ONa was stirred at
25 °C for 1 h. The methanol was evaporated under vacuum,
the crude diol obtained was dissolved in DMF (30 mL), and
then imidazole (3.53 mg, 58.7 mmol) and TBDMSCl (7.83 g,
51.7 mmol) were added under nitrogen. The reaction mixture
was stirred at room temperature for 48 h and then partitioned
between water (20 mL) and CH2Cl2 (100 mL). After separa-
tion, the organic layer was dried over sodium sulfate and
evaporated. The crude product was purified by column chro-
matography, eluting with petroleum ether/ethyl acetate (30:
Con clu sion
We have presented new reagent/catalyst systems for
the regio- and totally stereoselective synthesis of 2,3-
unsaturated C-arylglycosides. The reaction proceeds
under very mild conditions, and catalyst-controlled ste-
reoselection is observed in all cases. Palladium-catalyzed
coupling of p-tert-butylphenyl R-O-∆2-glycopyranoside
with various substituted arylmagnesium bromides pro-
vides the corresponding R-C-aryl-∆2-glycopyranosides,
while nickel-mediated reaction allows the â-C-aryl ano-
mers to be prepared. To the best of our knowledge,
overall retention of configuration with a “hard” organo-
metallic is realized for the first time. Application of this
coupling reaction to natural product synthesis and par-
ticularly to C-arylglycosides is now in progress in the
laboratory and will be presented in due course.
1) to give 5.1 g (90%) of 1b as an oil: Rf 0.42; [R]20 +107.0 (c
D
1
1.1, CH2Cl2); H NMR (200 MHz) δ 0.07 (s, 3H), 0.08 (s, 3H),
0.11 (s, 3H), 0.13 (s, 3H), 0.87 (s, 9H), 0.91 (s, 9H), 1.31 (s,
9H), 3.70-3.80 (m, 3H), 4.32 (brd, 1H, J ) 8.5 Hz), 5.61 (brs,
1H), 5.82 (brd, 1H, J ) 10.1 Hz), 6.00 (brd, 1H, J ) 10.1 Hz),
7.05 (d, 2H, J ) 8.8 Hz), 7.29 (d, 2H, J ) 8.8 Hz); 13C NMR
(50 MHz) δ -5.2, -4.9, -4.7, -4.1, 18.1, 18.6, 25.4, 26.1, 31.7,
34.3, 62.3, 63.6, 73.4, 93.4, 116.6, 124.9, 135.7, 144.7, 155.5.
Anal. Calcd for C28H50O4Si2: C, 66.35; H, 9.94. Found: C,
66.01; H, 9.89.
p-ter t-Bu tylp h en yl 6-O-(ter t-Bu tyld im eth ylsilyl)-2,3-
d id eoxy-â-D-er yth r o-h ex-2-en op yr a n osid e (21â). The so-
lution resulting from the recrystallization in the preparation
of p-tert-butylphenyl 4,6-di-O-acetyl-R-D-erythro-hex-2-enopy-
ranoside was evaporated and the mixture of R- and â-anomers
was deacetylated in methanol in the presence of a catalytic
amount of CH3ONa to give after evaporation of the solvent
p-tert-butylphenyl D-erythro-hex-2-enopyranoside as a mixture
of the two anomers. The crude mixture (7.5 g, 26.4 mmol) was
dissolved in CH2Cl2 (60 mL), and imidazole (90 mg, 1.3 mmol),
triethylamine (5.3 mL, 37.0 mmol), and TBDMSCl (5.44 g, 36.2
mmol) in CH2Cl2 (50 mL) were added at room temperature
under argon. The reaction mixture was stirred for 24 h and
then partitioned between water (100 mL) and CH2Cl2 (50 mL).
After separation, the organic layer was evaporated and the
residue was chromatographed eluting with petroleum ether/
Exp er im en ta l Section
Gen er a l Meth od s a n d Ma ter ia ls. All reactions were
monitored by thin-layer chromatography carried out on 0.2 mm
silica gel plates (60 F-254, Merck). Column chromatography
was performed on silica gel 60 (40-63 mesh ASTM, Macherey-
Nagel). NMR spectra were obtained in CDCl3, and chemical
shifts are given in ppm on the δ scale from internal tetram-
ethylsilane. THF was distilled from sodium/benzophenone,
purged, and kept under a nitrogen atmosphere. Reactions
involving palladium or nickel complexes were carried out in a
Schlenk tube under a nitrogen atmosphere. Tri-O-acetyl-D-
glucal, di-O-acetyl-L-rhamnal, bromoaryl compounds, phos-
phines, Pd2(dba)3, and TBDMSCl were purchased from Aldrich
Chemical Co.
diethyl ether (2:1) to give 3.11 g (30%) of 21â as an oil: Rf
1
0.30; [R]20 -14.7 (c 1.0, CH2Cl2); H NMR (200 MHz) δ 0.01
D
(s, 3H), 0.10 (s, 3H), 0.91 (s, 9H), 1.31 (s, 9H), 2.86 (d, 1H, J )
The following compounds were prepared by literature
methods: p-tert-butylphenyl 4,6-di-O-acetyl-2,3-dideoxy-R-D-
erythro-hex-2-enopyranoside,15 p-tert-butyl phenyl 4,6-di-O-
benzyl-2,3-dideoxy-R-D-erythro-hex-2-enopyranoside (1a),15 p-tert-
(22) Venanzi, L. M. J . Chem. Soc. 1958, 719.
(23) Van Hecke, G. R.; Horrocks, W. D., J r. Inorg. Chem. 1966, 5,
1968.
(24) Hayashi, T.; Konishi, M.; Yokota, K.; Kumada, M. Chem. Lett.
1986, 767.
(25) Levacher, V.; Moberg, C. J . Org. Chem. 1995, 60, 1755.
(26) Hatanaka, Y.; Yoshida, E.; Nakayama, H.; Kanaoka, Y. Bioorg.
Chem. 1989, 17, 482.
(19) Hudson, C. S. J . Am. Chem. Soc. 1909, 31, 66; 1930, 52, 1680;
1930, 52, 1707.
(20) Rockow, E. G. Inorg. Synth. 1960, 6, 218.
(21) Hayashi, T.; Konishi, M.; Kobori, Y.; Kumada, M.; Higuchi, T.;
Hirotsu, K. J . Am. Chem. Soc. 1984, 106, 158.
(27) Creany, X.; Aldridge, T. J . Org. Chem. 1991, 56, 4280.

588 J . Org. Chem., Vol. 63, No. 3, 1998
Moineau et al.
4.1 Hz), 3.77-3.95 (m, 3H), 4.33 (m, 1H), 5.75 (d, 1H, J ) 1.5
Hz), 5.92 (ddd, 1H, J ) 10.2, 1.5, 1.5 Hz), 6.11 (ddd, 1H, J )
10.2, 2.4, 1.6 Hz), 7.01 (d, 2H, J ) 8.8 Hz), 7.31 (d, 2H, J )
8.8 Hz); 13C NMR (50 MHz) δ -5.6, -5.5, 18.2, 25.9, 31.6, 34.2,
65.0, 65.7, 77.2, 94.8, 116.3, 126.2, 127.3, 132.0, 148.8, 154.8.
Anal. Calcd for C22H36O4Si: C, 67.30; H, 9.24. Found: C,
67.31; H, 9.28.
31.6, 34.2, 67.1, 69.3, 70.4, 71.4, 73.4, 93.2, 116.7, 126.3, 127.6,
127.7, 127.8, 127.9, 128.4, 128.8, 138.3, 138.4, 145.0, 155.2.
Anal. Calcd for C30H34O4: C, 78.57; H, 7.47. Found: C, 78.51;
H, 7.54.
p-ter t-Bu tylp h en yl 6-O-(ter t-Bu tyld im eth ylsilyl)-4-O-
m eth yl-2,3-d id eoxy-r-D-th r eo-h ex-2-en op yr a n osid e (24a ).
To compound 22 (1.7 g, 4.4 mmol) in THF (50 mL) was added
NaH (0.18 g, 6.6 mmol). After the solution was stirred for 15
min at 40 °C, CH3I (0.55 mL, 8.8 mmol) was added. After 24
h, the solution was hydrolyzed with water (10 mL) and
extracted with diethyl ether. Concentration of the solution
under vacuum and purification of the resulting oil by column
chromatography, eluting with petroleum ether/diethyl ether
p -ter t-Bu t ylp h en yl 4,6-Di-O-b en zyl-2,3-d id eoxy-â-D-
er yth r o-h ex-2-en op yr a n osid e (1a â). The unsaturated car-
bohydrate 21â (3.11 g, 7.8 mmol) was dissolved in THF (50
mL), and Bu4NF‚3H2O (2.5 g, 7.9 mmol) was added. The
reaction mixture was stirred for 2 h, and the solvent was
evaporated. The residue was partitioned between CH2Cl2 (100
mL) and water (30 mL). After separation, the organic larger
was dried and the solvent evaporated under reduced pressure
to give quantitatively p-tert-butylphenyl â-D-erythro-hex-2-
enopyranoside as an oil. The crude diol (2.17 g, 7.8 mmol) was
dissolved in toluol (10 mL), and NaOH 50% (6.2 mL) and n-Bu4-
NF‚3H2O (465 mg, 1.57 mmol) were added. A solution of
benzyl chloride (1.98 mL, 17.17 mmol) in toluol (5 mL) was
added slowly at 60 °C. The reaction mixture was stirred for
24 h, the toluol was evaporated, and the residue was parti-
tioned between diethyl ether (100 mL) and water (20 mL).
After evaporation of the solvent, the crude product was purified
by column chromatography, eluting with petroleum ether/ethyl
acetate (4:1) to give 3.25 g (91%) of compound 1a â as an oil:
(2/1), gave 1.61 g (yield 90%) of 24a as an oil: Rf 0.67; [R]20
D
-17.0 (c 1.0, CH2Cl2); 1H NMR (300 MHz) δ 0.02 (s, 3H), 0.05
(s, 3H), 0.85 (s, 9H), 1.30 (s, 9H), 3.45 (s, 3H), 3.63 (dd, 1H, J
) 5.2, 2.4 Hz), 3.73 (dd, 1H, J ) 9.9, 6.3 Hz), 3.89 (dd, 1H, J
) 9.9, 7.3 Hz), 4.21 (ddd, 1H, J ) 7.3, 6.3, 2.4 Hz), 5.73 (brd,
1H, J ) 2.9 Hz), 6.13 (dd, 1H, J ) 10.0, 2.9 Hz), 6.40 (brdd,
1H, J ) 10.0, 5.2 Hz), 7.05 (d, 2H, J ) 8.8 Hz), 7.30 (d, 2H, J
) 8.8 Hz); 13C NMR (50 MHz) δ -5.5, -5.4, 18.2, 25.9, 31.6,
34.2, 57.0, 61.7, 68.3, 71.8, 93.0, 116.5, 126.2, 127.7, 129.0,
149.1, 155.2. Anal. Calcd for C23H38O4Si: C, 67.94; H, 9.42.
Found: C, 68.17; H, 9.34.
p-ter t-Bu tylp h en yl 4-O-Meth yl-2,3-d id eoxy-r-D-th r eo-
h ex-2-en op yr a n osid e (24b). Compound 24b was obtained
by desilylation of compound 24a according to the same
procedure used for the desilylation of compound 23 (yield
Rf 0.55; [R]20 +9.6 (c 1.3, CH2Cl2); 1H NMR (200 MHz) δ 1.30
D
(s, 9H), 3.67 (dd, 1H, J ) 10.2, 6.0 Hz), 3.63 (dd, 1H, J ) 10.2,
5.7 Hz), 4.02 (dm, 1H, J ) 4.5 Hz), 4.21 (ddd, 1H, J ) 6.0, 5.7,
4.5 Hz), 4.49 (s, 2H), 4.60 (s, 2H), 5.76 (brs, 1H), 6.00 (ddd,
1H, J ) 10.2, 2.0, 1.1 Hz), 6.15 (ddd, 1H, J ) 10.2, 3.6, 1.3
Hz), 7.03 (d, 2H, J ) 8.8 Hz), 7.20-7.50 (m, 12H); 13C NMR
(50 MHz) δ 31.5, 34.1, 68.8, 70.0, 70.9, 73.3, 75.1, 93.3, 116.0,
126.2, 127.5, 127.6, 127.7, 127.8, 127.9, 128.0, 128.2, 128.3,
128.4, 128.5, 137.9, 138.2, 144.8, 154.8. Anal. Calcd for
100%): oil; Rf 0.35 (petroleum ether/ethyl acetate, 2:1); [R]20
D
-29.0 (c 1.1, CH2Cl2); 1H NMR (300 MHz) δ 1.30 (s, 9H), 3.44
(s, 3H), 3.69 (dd, 1H, J ) 5.1, 2.7 Hz), 3.74-3.79 (m, 1H), 3.81
(dd, 1H, J ) 11.8, 4.5 Hz), 3.95 (dd, 1H, J ) 11.8, 6.3 Hz),
4.23 (m, 1H), 5.79 (brd, 1H, J ) 2.9 Hz), 6.18 (dd, 1H, J )
10.1, 2.9 Hz), 6.37 (ddd, 1H, J ) 10.1, 5.1, 0.8 Hz), 7.04 (d,
2H, J ) 8.8 Hz), 7.31 (d, 2H, J ) 8.8 Hz); 13C NMR (50 MHz)
δ 31.5, 34.2, 56.6, 62.5, 69.7, 71.3, 93.0, 116.4, 126.4, 126.9,
129.4, 145.1, 154.9. Anal. Calcd for C17H24O4: C, 69.84; H,
8.27. Found: C, 69.41; H, 8.15.
C
30H34O4: C, 78.57; H, 7.47. Found: C, 78.49; H, 7.57.
p-ter t-Bu tylp h en yl 6-O-(ter t-Bu tyld im eth ylsilyl)-2,3-
d id eoxy-r-D-th r eo-h ex-2-en op yr a n osid e (22). To p-tert-
butylphenyl 6-O-(tert-butyldimethylsilyl)-2,3-dideoxy-R-D-erythro-
hex-2-enopyranoside (21) (0.39 g, 1.0 mmol) in toluol (10 mL)
was added PPh3 (0.52 g, 2.0 mmol) and ClCH2CO2H (0.19 g,
2.0 mmol). The solution was stirred for 15 min at 0 °C, and
DEAD (0.35 g, 2.0 mmol) was slowly added. After the solution
was stirred for 30 min at 0 °C, and 24 h at room temperature,
OPPh3 was separated and the solution was concentrated under
vacuum. The resulting oil was directly treated with a catalytic
amount of sodium methoxide in methanol (50 mL). After being
stirred for 1 h, the solution was concentrated under vacuum,
and the resulting oil was purified by column chromatography,
eluting with petroleum ether/diethyl ether (2:1) to give 0.32 g
p-ter t-Bu tylp h en yl 6-O-Ben zyl-4-O-m eth yl-2,3-d id eoxy-
r-D-th r eo-h ex-2-en op yr a n osid e (24c). Compound 24c was
prepared from p-tert-butylphenyl 4-O-methyl-2,3-dideoxy-R-
D-threo-hex-2-enopyranoside 24b according to the procedure
used for compound 1a â (yield 56%): oil; Rf 0.80 (petroleum
ether/ethyl acetate, 2:1); [R]20D -13.3 (c 1.1, CH2Cl2); 1H NMR
(200 MHz) δ 1.29 (s, 9H), 3.43 (s, 3H), 3.63 (dd, 1H, J ) 5.1,
2.6 Hz), 3.70 (dd, 1H, J ) 10.2, 6.6 Hz), 3.84 (dd, 1H, J ) 10.2,
6.1 Hz), 4.41 (ddd, 1H, J ) 6.6, 6.1, 2.6 Hz), 4.55 and 4.56 (2d,
2 × 1H, J ) 11.9 Hz), 5.71 (brd, 1H, J ) 3.0 Hz), 6.14 (dd, 1H,
J ) 10.1, 3.0 Hz), 6.36 (brdd, 1H, J ) 10.1, 5.1 Hz), 7.07 (d,
2H, J ) 8.8 Hz), 7.28 (d, 2H, J ) 8.8 Hz); 13C NMR (50 MHz)
δ 31.5, 34.1, 56.9, 67.0, 68.8, 69.2, 70.3, 93.2, 116.8, 126.2,
127.4, 127.4, 127.6, 127.8, 129.0, 138.3, 144.9, 155.1. Anal.
Calcd for C24H30O4: C, 75.36; H, 7.91. Found: C, 75.32; H,
7.87.
Gen er a l P r oced u r e for P a lla d iu m - a n d Nick el-Ca ta -
lyzed Rea ction . To a solution of the unsaturated carbohy-
drate (0.44 mmol) and PdCl2(dppf) (31.9 mg, 0.044 mmol) or
NiCl2(dppe) (23 mg, 0.044 mmol) in 2 mL of THF was added
at the desired temperature a solution of the Grignard reagent
prepared from magnesium (64 mg, 2.6 mmol) and the ap-
propriate bromide (2.18 mmol) in 5 mL of THF. The reaction
was followed by TLC. After the time indicated in the tables,
diethyl ether (50 mL) was added, and the ethereal solution
was washed with water (2 × 10 mL) and dried. Concentration
and column chromatography using the indicated solvents
furnished the C-glycosides.
(81%) of 22 as an oil: Rf 0.40; [R]20 +10.4 (c 1.0, CH2Cl2); 1H
D
NMR (200 MHz) δ 0.06 (s, 3H), 0.08 (s, 3H), 0.88 (s, 9H), 1.32
(s, 9H), 2.36 (d, 1H, J ) 7.3 Hz), 3.86 (dd, 1H, J ) 12.1, 6.1
Hz), 3.93 (dd, 1H, J ) 12.1, 6.1 Hz), 4.05 (ddd, 1H, J ) 7.3,
5.5, 2.2 Hz), 4.19 (ddd, 1H, J ) 6.1, 6.1, 2.2 Hz), 5.72 (d, 1H,
J ) 3.1 Hz), 6.06 (dd, 1H, J ) 9.9, 3.1 Hz), 6.32 (ddd, 1H, J )
9.9, 5.5, 0.6 Hz), 7.06 (d, 2H, J ) 8.9 Hz), 7.32 (d, 2H, J ) 8.9
Hz); 13C NMR (50 MHz) δ -5.4, -5.3, 18.3, 25.9, 31.6, 34.3,
61.9, 62.8, 71.1, 93.4, 116.6, 126.4, 127.8, 130.4, 145.0, 155.2.
Anal. Calcd for C22H36O4Si: C, 67.30; H, 9.24. Found: C,
67.12; H, 9.16.
p -ter t-Bu t ylp h en yl 4,6-Di-O-b en zyl-2,3-d id eoxy-r-D-
th r eo-h ex-2-en op yr a n osid e (23). To compound 22 (3.0 g,
7.9 mmol) in THF (50 mL) was added Bu4NF‚3H2O (2.5 g, 7.9
mmol). After being stirred for 2 h at room temperature, the
solution was treated with water (20 mL) and CH2Cl2 (100 mL).
Evaporation of the solvent gave quantitatively the correspond-
ing alcohol. This alcohol was benzylated according to the
procedure used for compound 1a â to give 1.88 g (yield 52%) of
(4,6-Di-O-ben zyl-2,3-d id eoxy-D-er yth r o-h ex-2-en op yr a -
n osyl)ben zen e (2a ). r-An om er : oil; Rf 0.41 (hexane/ethyl
23 as an oil: Rf 0.40 (petroleum ether/ethyl acetate, 8:1); [R]20
acetate, 4:1); [R]20 +18.5 (c 0.9, CH2Cl2); 1H NMR (300 MHz)
D
D
-42.3 (c 1.1, CH2Cl2); 1H NMR (200 MHz) δ 3.70-3.90 (m,
3H), 4.42 (dm, 1H, J ) 6.3 Hz), 4.67, 4.59, 4.54 and 4.48 (4d,
4 × 1H, J ) 11.9 Hz), 5.73 (brd, 1H, J ) 2.9 Hz), 6.11 (brdd,
1H, J ) 10.0, 2.9 Hz), 6.25 (brdd, 1H, J ) 10.0, 5.2 Hz), 7.07
(d, 2H, J ) 8.7 Hz), 7.20-7.40 (m, 12H); 13C NMR (50 MHz) δ
δ 3.50-3.70 (m, 3H), 4.19 (brd, 1H, J ) 7.3 Hz), 4.46 and 4.61
(2d, 2 × 1H, J ) 11.5 Hz), 4.43 and 4.58 (2d, 2 × 1H, J ) 12.1
Hz), 5.30 (brs, 1H), 6.06 (brd, 1H, J ) 10.9 Hz), 6.13 (brd, 1H,
J ) 10.9 Hz), 7.20-7.50 (m, 15H); 13C NMR (50 MHz) δ 69.1,
70.1, 70.7, 71.1, 73.2, 74.1, 127.1, 127.5, 127.7, 127.8, 127.9,

Synthesis of R- and â-C-Aryl ∆2-Glycopyranosides
J . Org. Chem., Vol. 63, No. 3, 1998 589
128.0, 128.1, 128.3, 128.3, 128.3, 129.5, 138.2, 138.2, 139.5.
Anal. Calcd for C26H26O3: C, 80.80; H, 6.78. Found: C, 80.37;
H, 6.69.
2H), 7.14 (d, 2H, J ) 8.7 Hz), 7.25 (d, 2H, J ) 8.7 Hz); 13C
NMR (50 MHz) δ -5.1, -5.0, -4.7, -4.2, 18.1, 18.5, 21.2, 25.9,
26.0, 62.7, 63.1, 77.2, 80.8, 127.0, 128.0, 129.99, 129.7, 130.8,
137.3, 138.4. Anal. Calcd for C25H44O3Si2: C, 66.91; H, 9.88.
Found: C, 66.63; H, 9.78.
â-An om er : oil; Rf 0.46 (petroleum ether/ethyl acetate, 5:1);
1
[R]20 +60.8 (c 0.7, CH2Cl2); H NMR (300 MHz) δ 3.60-3.90
D
(m, 3H), 4.16 (dm, 1H, J ) 8.6 Hz), 4.51 and 4.66 (2d, 2 × 1H,
J ) 11.5 Hz), 4.56 and 4.64 (2d, 2 × 1H, J ) 12.1 Hz), 5.18
(brs, 1H), 5.86 (ddd, 1H, J ) 10.3, 1.6, 1.6 Hz), 6.01 (ddd, 1H,
J ) 10.3, 2.0, 2.0 Hz), 7.20-7.40 (m, 15H); 13C NMR (50 MHz)
δ 69.9, 70.5, 71.2, 73.4, 77.4, 77.8, 125.8, 126.0, 127.1, 127.5,
127.9, 128.2, 128.3, 128.4, 128.5, 131.7, 138.1, 138.4, 140.8.
Anal. Calcd for C26H26O3: C, 80.80; H, 6.78. Found: C, 80.38;
H, 6.82.
1-(4,6-Di-O-ben zyl-2,3-dideoxy-r-D-er yth r o-h ex-2-en opy-
r a n osyl)-2-m eth ylben zen e (4a ): oil; Rf 0.50 (petroleum
ether/ethyl acetate, 5:1); [R]20D +38.1 (c 1.1, CH2Cl2); 1H NMR
(300 MHz) δ 2.16 (s, 3H), 3.50-3.70 (m, 3H), 4.22 (dt, 1H, J )
7.8, 2.0 Hz), 4.52 and 4.65 (2d, 2 × 1H, J ) 11.5 Hz), 4.43 and
4.55 (2d, 2 × 1H, J ) 12.2 Hz), 5.48 (m, 1H), 6.02 (ddd, 1H, J
) 10.4, 3.0, 1.6 Hz), 6.20 (dt, 1H, J ) 10.4, 2.0 Hz), 7.10-7.40
(m, 15H); 13C NMR (50 MHz) δ 19.2, 69.0, 70.4, 71.2, 71.6,
73.1, 125.2, 127.5, 127.7, 127.8, 127.9, 128.2, 128.4, 128.7,
129.8, 130.7, 136.7, 138.2, 138.3. Anal. Calcd for C27H28O3:
C, 80.97; H, 7.05. Found: C, 80.61; H, 7.14.
[4,6-Di-O-(ter t-bu tyldim eth ylsilyl)-2,3-dideoxy-D-er yth r o-
h ex-2-en op yr a n osyl]ben zen e (2b). r-An om er : oil; Rf 0.30
(petroleum ether/ethyl acetate, 30:1); [R]20 +3.9 (c 1.0, CH2-
D
1
Cl2); H NMR (200 MHz) δ 0.02 (s, 3H), 0.04 (s, 3H), 0.07 (s,
1-(4,6-Di-O-ben zyl-2,3-d id eoxy-D-er yth r o-h ex-2-en op y-
r a n osyl)-4-m eth oxyben zen e (5a ). r-An om er : oil; Rf 0.46
3H), 0.08 (s, 3H), 0.87 (s, 9H), 0.89 (s, 9H), 3.41 (ddd, 1H, J )
8.1, 6.2, 2.3 Hz), 3.70 (dd, 1H, J ) 11.1, 6.2 Hz), 3.85 (dd, 1H,
J ) 11.1, 2.3 Hz), 4.20 (dq, 1H, J ) 8.1, 1.9 Hz), 5.28 (m, 1H),
5.88 (ddd, 1H, J ) 10.3, 1.9, 1.9 Hz), 6.07 (ddd, 1H, J ) 10.3,
3.1, 1.7 Hz), 7.25-7.49 (m, 5H); 13C NMR (50 MHz) δ -5.2,
-5.0, -4.6, -4.0, 18.1, 18.5, 25.9, 26.1, 63.4, 64.3, 73.7, 74.6,
(petroleum ether/ethyl acetate, 5:1); [R]20 -3.8 (c 0.7, CH2-
D
Cl2); 1H NMR (300 MHz) δ 3.50-3.70 (m, 3H), 3.79 (s, 3H),
4.19 (dm, 1H, J ) 7.5 Hz), 4.48 and 4.62 (2d, 2 × 1H, J ) 11.4
Hz), 4.44 and 4.58 (2d, 2 × 1H, J ) 12.1 Hz), 5.26 (brs, 1H),
6.04 (ddd, 1H, J ) 10.4, 2.9, 1.5 Hz), 6.13 (dt, 1H, J ) 10.4,
1.8 Hz), 6.90 (brd, 2H, J ) 8.6 Hz), 7.20-7.40 (m, 14H); 13C
NMR (50 MHz) δ 55.3, 69.2, 70.3, 71.2, 73.3, 73.9, 113.7, 127.1,
127.6, 127.8, 127.9, 128.0, 128.3, 128.4, 129.6, 129.8, 131.6,
138.3, 159.4. Anal. Calcd for C27H28O4: C, 77.86; H, 6.78.
Found: C, 77.73; H, 6.67.
127.5, 127.6, 128.4, 128.5, 130.9, 140.4. Anal. Calcd for C24
42O3Si2: C, 66.30; H, 9.74. Found: C, 66.51; H, 9.84.
â-An om er : oil; Rf 0.52 (petroleum ether/ethyl acetate, 30:
-
H
1); [R]20D +189.1 (c 1.0, CH2Cl2); 1H NMR (200 MHz) δ 0.04 (s,
6H), 0.13 (s, 3H), 0.14 (s, 3H), 0.90 (s, 9H), 0.93 (s, 9H), 3.51
(ddd, 1H, J ) 8.5, 4.5, 2.1 Hz), 3.84 (dd, 1H, J ) 11.4, 4.5 Hz),
3.93 (dd, 1H, J ) 11.4, 2.1 Hz), 4.38 (dd, 1H, J ) 8.5, 2.9 Hz),
5.16 (d, 1H, J ) 2.9 Hz), 5.77 (s, 2H), 7.27-7.36 (m, 5H); 13C
NMR (50 MHz) δ -5.0, -4.9, -4.6, -4.1, 18.2, 18.6, 26.0, 26.1,
63.1, 63.6, 77.3, 80.7, 127.1, 127.8, 128.4, 129.9, 130.7, 141.5.
Anal. Calcd for C24H42O3Si2: C, 66.30; H, 9.74. Found: C,
66.00; H, 9.71.
â-An om er : oil; Rf 0.40 (petroleum ether/ethyl acetate, 5:1);
[R]20 +175.8 (c 1.0, CH2Cl2); 1H NMR (200 MHz) δ 3.80 (s,
D
3H), 3.60-3.90 (m, 3H), 4.15 (dm, 1H, J ) 8.7 Hz), 4.51 and
4.66 (2d, 2 × 1H, J ) 11.5 Hz), 4.55 and 4.63 (2d, 2 × 1H, J
) 12.2 Hz), 5.14 (brs, 1H), 5.84 (brd, 1H, J ) 10.3 Hz), 6.01
(brd, 1H, J ) 10.3 Hz), 6.89 (brd, 2H, J ) 8.6 Hz), 7.20-7.40
(m, 12H); 13C NMR (50 MHz) δ 55.5, 70.2, 70.8, 71.5, 73.6,
77.3, 78.1, 114.1, 126.2, 127.7, 128.0, 128.2, 128.4, 128.5, 128.6,
128.8, 132.1, 133.2, 138.3, 138.7, 159.6. Anal. Calcd for
1-(4,6-Di-O-ben zyl-2,3-d id eoxy-D-er yth r o-h ex-2-en op y-
r a n osyl)-4-m eth ylben zen e (3a ). r-An om er : oil; Rf 0.62
(hexane/ethyl acetate, 5:1); [R]20D -2.6 (c 1.1, CH2Cl2); 1H NMR
(200 MHz) δ 2.2 (s, 3H), 3.50-3.70 (m, 3H), 4.21 (brd, 1H, J )
7.0 Hz), 4.44 and 4.59 (2d, 2 × 1H, J ) 12.1 Hz), 4.48 and
4.62 (2d, 2 × 1H, J ) 11.5 Hz), 5.30 (brs, 1H), 6.06 (dm, 1H,
J ) 10.4 Hz), 6.14 (dm, 1H, J ) 10.4 Hz), 7.10-7.40 (m, 14H);
13C NMR (50 MHz) δ 21.1, 69.2, 70.2, 70.5, 71.1, 73.2, 74.0,
127.0, 127.5, 127.7, 127.85, 127.9, 128.1, 128.3, 128.4, 129.0,
129.7, 136.4, 137.6, 138.2. Anal. Calcd for C27H28O3: C, 80.97;
H, 7.05. Found: C, 80.48; H, 7.35.
C
27H28O4: C, 77.86; H, 6.78. Found: C, 77.32; H, 6.49.
1-(4,6-Di-O-ben zyl-2,3-d id eoxy-D-er yth r o-h ex-2-en op y-
r a n osyl)-3-m eth oxyben zen e (6a ). r-An om er : oil; Rf 0.40
(petroleum ether/ethyl acetate, 5:1); [R]20 +9.1 (c 1.0, CH2-
D
Cl2); 1H NMR (300 MHz) δ 3.63-3.75 (m, 3H), 3.75 (s, 3H),
4.17 (brd, 1H, J ) 7.9 Hz), 4.47 and 4.59 (2d, 2 × 1H, J ) 12.0
Hz), 4.49 and 4.62 (2d, 2 × 1H, J ) 12.0 Hz), 5.28 (brs, 1H),
6.11 (s, 2H), 6.83 (dd, 1H, J ) 8.4, 2.0 Hz), 6.99 (brd, 1H, J )
7.9 Hz), 7.02 (d, 1H, J ) 2.0 Hz), 7.21-7.32 (m, 11H); 13C NMR
(50 MHz) δ 55.2, 69.5, 70.5, 71.1, 71.3, 73.6, 74.2, 113.3, 113.5,
120.2, 127.1, 127.6, 127.7, 127.9, 128.3, 128.4, 129.3, 129.6,
138.2, 141.2, 159.7. Anal. Calcd for C27H28O4: C, 77.86; H,
6.78. Found: C, 77.69; H, 6.69.
â-An om er : oil; Rf 0.54 (petroleum ether/ethyl acetate, 5:1);
[R]20 +171.0 (c 1.0, CH2Cl2); 1H NMR (200 MHz) δ 2.33 (s,
D
3H), 3.70-3.90 (m, 3H), 4.15 (dm, 1H, J ) 8.4 Hz), 4.51 and
4.66 (2d, 2 × 1H, J ) 11.5 Hz), 4.55 and 4.63 (2d, 2 × 1H, J
) 12.3 Hz), 5.15 (brs, 1H), 5.84 (dt, 1H, J ) 10.3, 1.4 Hz), 6.00
(ddd, 1H, J ) 10.3, 2.0, 1.8 Hz), 7.10-7.40 (m, 14H); 13C NMR
(50 MHz) δ 21.3, 70.1, 70.7, 71.3, 73.5, 77.4, 78.0, 126.0, 127.2,
127.6, 127.9, 128.0, 128.4, 129.2, 131.9, 137.7, 137.9, 138.2,
138.6. Anal. Calcd for C27H28O3: C, 80.97; H, 7.05. Found:
C, 80.54; H, 7.20.
â-An om er : oil; Rf 0.46 (petroleum ether/ethyl acetate, 5:1);
[R]20D +169.0 (c 0.9, CH2Cl2); 1H NMR (300 MHz) δ 3.71-3.86
(m, 3H), 3.79 (s, 3H), 4.16 (dm, 1H, J ) 8.7 Hz), 4.52 and 4.66
(2d, 2 × 1H, J ) 11.5 Hz), 4.57 and 4.63 (2d, 2 × 1H, J ) 12.3
Hz), 5.17 (m, 1H), 5.86 (ddd, 1H, J ) 10.4, 1.7, 1.5 Hz), 6.00
(ddd, 1H, J ) 10.4, 2.2, 1.9 Hz), 6.82 (dd, 1H, J ) 8.3, 2.7 Hz),
6.91 (brs, 1H), 6.93 (brd, 1H), 7.22-7.37 (m, 11H); 13C NMR
(50 MHz) δ 55.3, 70.0, 70.6, 71.3, 73.5, 77.4, 77.9, 112.7, 113.6,
119.5, 126.1, 127.6, 127.9, 128.0, 128.4, 128.5, 129.6, 131.7,
138.1, 138.5, 142.4, 159.8. Anal. Calcd for C27H28O4: C, 77.86;
H, 6.78. Found: C, 77.57; H, 6.68.
1-[4,6-Di-O-(ter t-bu tyldim eth ylsilyl)-2,3-dideoxy-D-er yth -
r o-h ex-2-en op yr a n osyl]-4-m et h ylb en zen e (3b ). r-An o-
m er : oil; Rf 0.38 (petroleum ether/ethyl acetate, 30:1); [R]20
D
1
-3.1 (c 1.3, CH2Cl2); H NMR (300 MHz) δ 0.02 (s, 3H), 0.03
(s, 3H), 0.07 (s, 3H), 0.10 (s, 3H), 0.86 (s, 9H), 0.88 (s, 9H),
2.33 (s, 3H), 3.40 (ddd, 1H, J ) 8.0, 6.2, 2.3 Hz), 3.68 (dd, 1H,
J ) 11.1, 2.3 Hz), 3.82 (dd, 1H, J ) 11.1, 6.2 Hz), 4.16 (dm,
1H, J ) 8.0 Hz), 5.23 (brs, 1H), 5.86 (ddd, 1H, J ) 10.4, 3.1,
1.8 Hz), 6.03 (dt, 1H, J ) 10.4, 1.8 Hz), 7.14 (d, 2H, J ) 7.5
Hz), 7.33 (d, 2H, J ) 7.5 Hz); 13C NMR (50 MHz) δ -5.2, -5.0,
-4.6, -4.0, 18.1, 18.5, 21.2, 25.9, 26.1, 63.4, 64.3, 73.6, 74.3,
1-(4,6-Di-O-ben zyl-2,3-d id eoxy-D-er yth r o-h ex-2-en op y-
r a n osyl)-2-m eth oxyben zen e (7a ). r-An om er : oil; Rf 0.44
(petroleum ether/ethyl acetate, 5:1); [R]20 +15.5 (c 1.0,
D
CH2Cl2); 1H NMR (300 MHz) δ 3.66 (dd, 1H, J ) 10.5, 3.4 Hz),
3.70 (dd, 1H, J ) 10.5, 4.6 Hz), 3.83 (s, 3H), 3.87 (ddd, 1H, J
) 7.4, 4.6, 3.4 Hz), 4.09 (brd, 1H, J ) 7.4 Hz), 4.48 and 4.57
(2d, 2 × 1H, J ) 12.0 Hz), 4.52 and 4.65 (2d, 2 × 1H, J ) 11.4
Hz), 5.69 (brs, 1H), 6.02 (ddd, 1H, J ) 10.4, 2.6, 1.3 Hz), 6.10
(ddd, 1H, J ) 10.4, 1.8, 1.8 Hz), 6.89 (d, 1H, J ) 8.2 Hz), 6.91
(dd, 1H, J ) 7.5, 7.5 Hz), 7.20-7.30 (m, 11H), 7.44 (dd, 1H, J
) 7.5, 1.6 Hz); 13C NMR (50 MHz) δ 55.6, 68.8, 69.4, 70.3, 70.9,
71.5, 73.2, 110.8, 120.1, 126.3, 127.4, 127.5, 127.7, 127.8, 127.9,
127.6, 128.6, 129.0, 130.8, 137.1, 137.4. Anal. Calcd for C25
44O3Si2: C, 66.91; H, 9.88. Found: C, 66.50; H, 9.81.
-
H
â-An om er : oil; Rf 0.40 (petroleum ether/ethyl acetate, 30:
1); [R]20D +145.5 (c 1.1, CH2Cl2); 1H NMR (200 MHz) δ 0.04 (s,
6H), 0.14 (s, 3H), 0.15 (s, 3H), 0.90 (s, 9H), 0.94 (s, 9H), 2.35
(s, 3H), 3.51 (ddd, 1H, J ) 8.5, 4.6, 1.9 Hz), 3.84 (brdd, 1H, J
) 11.4, 4.6 Hz), 3.93 (brdd, 1H, J ) 11.4, 1.9 Hz), 4.38 (brdd,
1H, J ) 8.5, 2.8 Hz), 5.13 (brd, 1H, J ) 2.8 Hz), 5.76 (brs,

590 J . Org. Chem., Vol. 63, No. 3, 1998
Moineau et al.
128.3, 128.4, 128.6, 129.2, 130.3, 138.4, 138.4, 157.4. Anal.
Calcd for C27H28O4: C, 77.86; H, 6.78. Found: C, 77.44; H,
6.69.
â-An om er : oil; Rf 0.60 (petroleum ether/ethyl acetate, 5:1);
D
[R]20 +123.8 (c 1.0, CH2Cl2); 1H NMR (200 MHz) δ 0.16 (s,
6H), 0.96 (s, 9H), 3.60-3.84 (m, 3H), 4.13 (dm, 1H, J ) 8.2
Hz), 4.49 and 4.54 (2d, 2 × 1H, J ) 11.5 Hz), 4.62 and 4.64
(2d, 2 × 1H, J ) 12.1 Hz), 5.12 (brs, 1H), 5.83 (ddd, 1H, J )
10.3, 1.5, 1.3 Hz), 5.98 (dt, 1H, J ) 10.3, 1.9 Hz), 6.78 (d, 2H,
â-An om er : oil; Rf 0.50 (petroleum ether/ethyl acetate, 5:1);
[R]20 +151.0 (c 1.3, CH2Cl2); 1H NMR (200 MHz) δ 3.83 (s,
D
3H), 3.70-3.90 (m, 3H), 4.17 (dm, 1H, J ) 8.5 Hz), 4.52 and
4.66 (2d, 2 × 1H, J ) 11.5 Hz), 4.59 and 4.67 (2d, 2 × 1H, J
) 12.3 Hz), 5.61 (brs, 1H), 5.89 (brd, 1H, J ) 10.8 Hz), 5.94
(brd, 1H, J ) 10.8 Hz), 6.80-7.10 (m, 3H), 7.20-7.50 (m, 11H);
13C NMR (50 MHz) δ 55.5, 70.1, 70.7, 71.2, 71.6, 73.4, 78.0,
110.3, 120.9, 125.3, 127.3, 127.5, 127.8, 128.0, 128.4, 128.5,
128.6, 131.8, 138.3, 138.7, 156.1. Anal. Calcd for C27H28O4:
C, 77.86; H, 6.78. Found: C, 77.63; H, 6.50.
J ) 8.5 Hz), 7.19 (d, 2H, J ) 8.5 Hz), 7.20-7.34 (m, 10H); 13
C
NMR (50 MHz) δ -4.2, 18.3, 25.9, 70.1, 70.7, 71.4, 73.6, 77.3,
78.1, 120.2, 126.1, 127.7, 127.9, 128.0, 128.1, 128.5, 128.6,
128.7, 132.1, 133.8, 138.3, 138.6, 155.6. Anal. Calcd for C32
40O4Si: C, 74.38; H, 7.80. Found: C, 73.79; H, 7.90.
4-[(ter t-Bu t yld im et h ylsilyl)oxy]-1-[4,6-d i-O-(ter t-b u -
-
H
tyld im eth ylsilyl)-2,3-d id eoxy-â-D-er yth r o-h ex-2-en op yr a -
n osyl]ben zen e (10b): oil; Rf 0.31 (petroleum ether/dichlo-
1-(4,6-Di-O-ben zyl-2,3-d id eoxy-D-er yth r o-h ex-2-en op y-
r a n osyl)-3,4-(m eth ylen ed ioxy)ben zen e (8a ). r-An om er :
oil; Rf 0.37 (hexane/ethyl acetate, 4:1); [R]20D +11.7 (c 0.8, CH2-
1
romethane, 5:1); [R]20 +101.2 (c 1.0, CH2Cl2); H NMR (200
D
MHz) δ -0.07 (s, 3H), -0.06 (s, 3H), 0.04 (s, 3H), 0.06 (s, 3H),
0.10 (s, 6H), 0.80 (s, 9H), 0.84 (s, 9H), 0.90 (s, 9H), 3.40 (ddd,
1H, J ) 8.4, 4.6, 2.0 Hz), 3.73 (dd, 1H, J ) 11.4, 4.6 Hz), 3.83
(dd, 1H, J ) 11.4, 2.0 Hz), 4.27 (dd, 1H, J ) 8.4, 2.9 Hz), 5.00
(brd, 1H, J ) 2.9 Hz), 5.68 (s, 2H), 6.71 (brd, 2H, J ) 8.5 Hz),
7.11 (brd, 2H, J ) 8.5 Hz); 13C NMR (50 MHz) δ -5.1, -5.0,
-4.7, -4.4, -4.2, 18.1, 18.3, 18.5, 25.8, 25.9, 26.0, 63.0, 63.6,
76.8, 80.7, 119.9, 128.3, 129.8, 130.7, 134.1, 155.2. Anal. Calcd
for C30H56O4Si3: C, 63.77; H, 9.99. Found: C, 64.06; H, 10.11.
1-(4,6-Di-O-ben zyl-2,3-dideoxy-r-D-er yth r o-h ex-2-en opy-
r a n osyl)-4-(d im eth oxym eth yl)ben zen e (11a ): oil; Rf 0.31
1
Cl2); H NMR (200 MHz) δ 3.50-3.70 (m, 3H), 4.19 (dm, 1H,
J ) 7.1 Hz), 4.47 and 4.61 (2d, 2 × 1H, J ) 11.5 Hz), 4.44 and
4.58 (2d, 2 × 1H, J ) 12.1 Hz), 5.20 (brs, 1H), 5.91 (s, 2H),
6.01 (ddd, 1H, J ) 10.4, 2.5, 1.2 Hz), 6.12 (ddd, 1H, J ) 10.4,
1.7, 1.7 Hz), 6.75 (d, 1H, J ) 8.0 Hz), 6.90 (dd, 1H, J ) 8.0,
1.4 Hz), 6.95 (d, 1H, J ) 1.4 Hz), 7.20-7.40 (m, 10H); 13C NMR
(50 MHz) δ 69.1, 70.1, 70.4, 71.1, 73.3, 73.9, 101.0, 107.9, 108.8,
121.8, 125.2, 127.2, 127.5, 127.7, 127.8, 127.9, 128.0, 128.1,
128.1, 128.3, 128.4, 129.5. Anal. Calcd for C27H26O5: C, 75.33;
H, 6.09. Found: C, 75.29; H, 6.01.
(petroleum ether/ethyl acetate, 5:1); [R]20 +4.1 (c 1.0, CH2-
D
â-An om er : oil; Rf 0.38 (petroleum ether/ethyl acetate, 5:1);
[R]20D +162.5 (c 1.0, CH2Cl2); 1H NMR (200 MHz) δ 3.70-3.90
(m, 3H), 4.16 (dm, 1H, J ) 8.3 Hz), 4.52 and 4.68 (2d, 2 × 1H,
J ) 11.5 Hz), 4.57 and 4.64 (2d, 2 × 1H, J ) 12.2 Hz), 5.12
(brs, 1H), 5.84 (ddd, 1H, J ) 10.3, 2.2, 1.8 Hz), 5.95 (s, 2H),
6.01 (dt, 1H, J ) 10.3, 1.6 Hz), 6.78 (dd, 1H, J ) 7.5, 1.0 Hz),
6.82 (d, 1H, J ) 1.0 Hz), 6.84 (d, 1H, J ) 7.5 Hz), 7.20-7.40
(m, 10H); 13C NMR (50 MHz) δ 70.0, 70.6, 71.4, 73.5, 77.3,
77.9, 101.1, 108.0, 108.2, 120.9, 126.3, 127.6, 127.9, 127.9,
128.0, 128.4, 128.5, 131.7, 134.8, 138.1, 138.5, 147.4, 147.8.
Anal. Calcd for C27H26O5: C, 75.33; H, 6.09. Found: C, 75.20;
H, 6.02.
Cl2); 1H NMR (200 MHz) δ 3.33 (s, 6H), 3.57-3.74 (m, 3H),
4.20 (brd, 1H, J ) 8.1 Hz), 4.47 and 4.61 (2d, 2 × 1H, J ) 12.1
Hz), 4.50 and 4.64 (2d, 2 × 1H, J ) 11.5 Hz), 5.31 (s, 1H),
5.39 (s, 1H), 6.09 (d, 1H, J ) 10.5 Hz), 6.16 (d, 1H, J ) 10.5
Hz), 7.27-7.44 (m, 14H); 13C NMR (50 MHz) δ 52.6, 69.2, 70.1,
70.8, 71.1, 73.2, 73.8, 102.9, 126.7, 126.8, 127.2, 127.5, 127.7,
127.8, 127.8, 127.9, 128.3, 128.4, 129.5, 137.7, 138.2, 138.2,
139.8. Anal. Calcd for C29H32O5: C, 75.63; H, 7.00. Found:
C, 75.45; H, 7.14.
1-[4,6-Bis-O-(ter t-bu tyld im eth ylsilyl)-2,3-d id eoxy-â-D-
er yth r o-h ex-2-en op yr a n osyl]-4-(m et h oxym et h oxy)b en -
zen e (12a ). â-An om er : oil; Rf 0.37 (petroleum ether/diethyl
ether, 30:1); [R]20D +160.4 (c 1.0, CH2Cl2); 1H NMR (200 MHz)
δ 0.04 (s, 6H), 0.14 (s, 3H), 0.15 (s, 3H), 0.90 (s, 9H), 0.94 (s,
9H), 3.49 (s, 3H), 3.50 (m, 1H), 3.83 (dd, 1H, J ) 11.4, 4.4
Hz), 3.92 (dd, 1H, J ) 11.4, 1.9 Hz), 4.36 (brdd, 1H, J ) 8.6,
2.9 Hz), 5.12 (brd, 1H, J ) 2.4 Hz), 5.19 (s, 2H), 5.76 (brs,
2H), 7.01 (d, 2H, J ) 8.5 Hz), 7.28 (d, 2H, J ) 8.5 Hz); 13C
NMR (50 MHz) δ -5.1, -5.0, -4.7, -4.2, 18.1, 18.5, 25.9, 26.0,
55.9, 62.9, 63.5, 76.8, 80.7, 94.5, 116.1, 128.3, 129.8, 130.7,
134.8, 156.9. Anal. Calcd for C26H46O5Si2: C, 63.11; H, 9.37.
Found: C, 63.53; H, 9.56.
1-(4,6-Di-O-ben zyl-2,3-dideoxy-r-D-er yth r o-h ex-2-en opy-
r a n osyl)-4-ch lor oben zen e (9a ). r-An om er : oil; Rf 0.42
(petroleum ether/ethyl acetate, 5:1); [R]20 +1.9 (c 0.9, CH2-
D
1
Cl2); H NMR (200 MHz) δ 3.50-3.70 (m, 3H), 4.17 (dm, 1H,
J ) 7.4 Hz), 4.46 and 4.59 (2d, 2 × 1H, J ) 12.1 Hz), 4.48 and
4.62 (2d, 2 × 1H, J ) 11.5 Hz), 5.28 (brs, 1H), 6.05 (ddd, 1H,
J ) 10.4, 2.7, 1.3 Hz), 6.15 (dt, 1H, J ) 10.4, 1.8 Hz), 7.20-
7.40 (m, 14H); 13C NMR (50 MHz) δ 69.1, 70.0, 70.8, 71.3, 73.3,
73.4, 127.6, 128.9, 128.0, 128.3, 128.4, 128.5, 129.1, 129.4,
133.8, 138.1. Anal. Calcd for C26H25O3Cl: C, 74.19; H, 5.99.
Found: C, 73.92; H, 5.82.
1-(4,6-Di-O-ben zyl-2,3-dideoxy-r-D-er yth r o-h ex-2-en opy-
1-[4,6-Di-O-(ter t-b u t yld im et h ylsilyl)-2,3-d id eoxy-â-D-
r a n osyl)-4-vin ylben zen e (13a ): oil; Rf 0.50 (petroleum ether/
1
ethyl acetate 5:1); [R]20 -26.5 (c 1.0, CH2Cl2); H NMR (300
er yth r o-h ex-2-en op yr a n osyl]-4-ch lor ob en zen e
(9b ).
D
â-An om er : oil; Rf 0.49 (petroleum ether/dichloromethane, 10:
3); [R]20D +190.1 (c 1.0, CH2Cl2); 1H NMR (200 MHz) δ 0.03 (s,
6H), 0.13 (s, 3H), 0.14 (s, 3H), 0.90 (s, 9H), 0.93 (s, 9H), 3.49
(ddd, 1H, J ) 8.4, 4.4, 2.2 Hz), 3.83 (dd, 1H, J ) 11.4, 4.4 Hz),
3.92 (dd, 1H, J ) 11.4, 2.2 Hz), 4.37 (ddt, 1H, J ) 8.4, 3.0, 1.5
Hz), 5.13 (brs, 1H), 5.71 (dt, 1H, J ) 10.2, 1.5 Hz), 5.80 (ddd,
1H, J ) 10.2, 1.5, 1.5 Hz), 7.24-7.34 (m, 4H); 13C NMR (50
MHz) δ -5.0, -4.9, -4.7, -4.2, 18.1, 18.6, 25.9, 26.1, 62.9, 63.4,
76.6, 80.7, 128.5, 128.6, 130.1, 130.4, 133.5, 140.0. Anal. Calcd
for C24H41O3Si2Cl: C, 61.44; H, 8.81. Found: C, 61.55; H, 8.92.
MHz) δ 3.57-3.71 (m, 3H), 4.20 (dm, 1H, J ) 7.5 Hz), 4.46
and 4.59 (2d, 2 × 1H, J ) 12.1 Hz), 4.48 and 4.62 (2d, 2 × 1H,
J ) 11.5 Hz), 5.25 (dd, 1H, J ) 10.9, 0.9 Hz), 5.30 (m, 1H),
5.75 (dd, 1H, J ) 17.6, 0.9 Hz), 6.08 (ddd, 1H, J ) 10.4, 2.7,
1.4 Hz), 6.14 (dt, 1H, J ) 10.4, 1.7 Hz), 6.71 (dd, 1H, J ) 17.6,
10.9 Hz), 7.23-7.43 (m, 10H); 13C NMR (50 MHz) δ 69.4, 70.4,
71.0, 71.4, 73.5, 74.2, 114.3, 126.4, 127.5, 127.8, 128.0, 128.1,
128.2, 128.6, 128.6, 128.6, 129.7, 136.7. Anal. Calcd for
C
28H28O3: C, 81.52; H, 6.84. Found: C, 81.31; H, 6.81.
2-(4,6-Di-O-ben zyl-2,3-dideoxy-r-D-er yth r o-h ex-2-en opy-
4-[(ter t-Bu tyld im eth ylsilyl)oxy]-1-(4,6-d i-O-ben zyl-2,3-
d id eoxy-D-er yth r o-h ex-2-en op yr a n osyl)b en zen e (10a ).
r-An om er : oil; Rf 0.53 (petroleum ether/ethyl acetate, 5:1);
r a n osyl)th iop h en e (14a ): oil; Rf 0.24 (petroleum ether/ethyl
acetate, 5:1); [R]20 +22.4 (c 1.2, CH2Cl2); 1H NMR (200 MHz)
D
δ 3.50-3.80 (m, 3H), 4.24 (brd, 1H, J ) 8.3 Hz), 4.45 and 4.60
(2d, 2 × 1H, J ) 12.1 Hz), 4.47 and 4.61 (2d, 2 × 1H, J ) 11.4
Hz), 5.50 (brs, 1H), 6.08 (d, 1H, J ) 11.0 Hz), 6.14 (d, 1H, J )
11.0 Hz), 6.90-7.00 (m, 2H), 7.20-7.30 (m, 11H); 13C NMR
(50 MHz) δ 69.0, 70.1, 70.2, 70.5, 71.2, 73.3, 126.0, 126.6, 126.8,
127.5, 127.6, 127.7, 127.7, 127.8, 127.9, 127.3, 128.1, 128.3,
128.4, 128.6, 138.1, 138.2, 142.9. Anal. Calcd for C24H24O3S:
C, 73.44; H, 6.16. Found: C, 73.18; H, 5.98.
[R]20 -9.2 (c 1.0, CH2Cl2); 1H NMR (200 MHz) δ 0.19 (s, 6H),
D
0.99 (s, 9H), 3.58-3.71 (m, 3H), 3.95 (brd, 1H, J ) 7.2 Hz),
4.45 and 4.60 (2d, 2 × 1H, J ) 12.1 Hz), 4.56 and 4.64 (2d, 2
× 1H, J ) 11.9 Hz), 5.27 (brs, 1H), 6.05 (dm, 1H, J ) 10.5
Hz), 6.16 (dm, 1H, J ) 10.5 Hz), 6.80 (brd, 2H, J ) 8.5 Hz),
7.27-7.32 (m, 12H); 13C NMR (50 MHz) δ -4.3, 18.3, 25.8,
69.3, 70.3, 70.4, 71.2, 73.3, 73.9, 119.9, 127.1, 127.6, 127.8,
127.9, 128.0, 128.4, 128.5, 129.6, 129.9, 132.3, 138.3, 138.3,
1-(4,6-Di-O-ben zyl-2,3-dideoxy-r-D-er yth r o-h ex-2-en opy-
155.5. Anal. Calcd for
Found: C, 74.01; H, 7.75.
C32H40O4Si: C, 74.38; H, 7.80.
r a n osyl)n a p h th a len e (15a ): oil; Rf 0.38 (petroleum ether/
ethyl acetate, 5:1); [R]20 -73.8 (c 1.0, CH2Cl2); 1H NMR (300
D

Synthesis of R- and â-C-Aryl ∆2-Glycopyranosides
J . Org. Chem., Vol. 63, No. 3, 1998 591
MHz) δ 3.59-3.76 (m, 3H), 4.25 (brdd, 1H, J ) 7.8, 2.0 Hz),
4.46 and 4.60 (2d, 2 × 1H, J ) 12.1 Hz), 4.51 and 4.65 (2d, 2
× 1H, J ) 11.5 Hz), 5.47 (brs, 1H), 6.21 (s, 2H), 7.25-7.34 (m,
10H), 7.45-7.49 (m, 2H), 7.59 (dd, 1H, J ) 8.4, 1.5 Hz), 7.78-
7.85 (m, 4H); 13C NMR (50 MHz) δ 69.5, 70.6, 71.0, 71.5, 73.6,
74.5, 126.2, 126.4, 127.0, 127.6, 127.6, 127.8, 127.9, 128.0,
128.3, 128.4, 128.5, 129.5, 133.1, 133.1, 137.0, 138.2, 138.3.
Anal. Calcd for C30H28O3: C, 82.54; H, 6.47. Found: C, 82.11;
H, 6.45.
135.6, 138.3, 138.4. Anal. Calcd for C22H24O3: C, 78.54; H,
7.19. Found: C, 78.09; H, 7.11.
(4-O-Ben zyl-2,3,6-tr id eoxy-L-er yth r o-h ex-2-en op yr a n o-
syl)ben zen e (25). r-An om er : oil; Rf 0.66 (petroleum ether/
ethyl acetate, 5:1); [R]20 -20.6 (c 1.0, CH2Cl2); 1H NMR (200
D
MHz) δ 1.25 (d, 3H, J ) 6.0 Hz), 3.69-3.77 (m, 2H), 4.60 and
4.70 (2d, 2 × 1H, J ) 11.6 Hz), 5.21 (s, 1H), 6.07 (brd, 1H, J
) 11.3 Hz), 6.14 (brd, 1H, J ) 11.3 Hz), 7.25-7.45 (m, 10H);
13C NMR (50 MHz) δ 18.4, 67.9, 71.1, 73.7, 75.8, 126.7, 127.9,
128.0, 128.1, 128.1, 128.5, 128.7, 130.3, 138.5, 140.1. Anal.
Calcd for C19H20O2: C, 81.40; H, 7.19. Found: C, 81.23; H,
7.15.
r-(4,6-Di-O-ben zyl-2,3-dideoxy-r-D-er yth r o-h ex-2-en opy-
r a n osyl)tolu en e (16a ): oil; Rf 0.48 (hexane/ethyl acetate,
1
5:1); [R]20 +78.4 (c 1.0, CH2Cl2); H NMR (300 MHz) δ 2.82
D
(dd, 1H, J ) 13.5, 7.6 Hz), 3.08 (dd, 1H, J ) 13.5, 6.8 Hz),
3.71 (d, 2H, J ) 3.8 Hz), 3.91 (dt, 1H, J ) 7.4, 3.8 Hz), 4.01
(dm, 1H, J ) 7.4 Hz), 4.42 (m, 1H), 4.52 and 4.62 (2d, 2 × 1H,
J ) 12.0 Hz), 4.48 and 4.60 (2d, 2 × 1H, J ) 11.2 Hz), 5.80
(ddd, 1H, J ) 10.5, 2.7, 1.6 Hz), 5.95 (dt, 1H, J ) 10.5, 2.1
Hz), 7.10-7.40 (m, 15H); 13C NMR (50 MHz) δ 39.7, 69.4, 70.1,
71.3, 72.0, 73.3, 73.7, 125.7, 126.3, 127.5, 127.7, 127.8, 127.9,
128.3, 128.3, 128.4, 129.4, 130.9, 138.1, 138.2. Anal. Calcd
for C27H28O3: C, 80.97; H, 7.05. Found: C, 80.43; H, 7.10.
3-(4,6-Di-O-ben zyl-2,3-dideoxy-r-D-er yth r o-h ex-2-en opy-
r a n osyl)p r op en e (17a ): oil; Rf 0.52 (petroleum ether/ethyl
â-An om er : oil; Rf 0.70 (petroleum ether/ethyl acetate, 5:1);
D
1
[R]20 -219.2 (c 1.0, CH2Cl2); H NMR (200 MHz) δ 1.38 (d,
3H, J ) 5.9 Hz), 3.73 (dq, 1H, J ) 8.4, 5.9 Hz), 3.85 (dm, 1H,
J ) 8.4 Hz), 4.60 and 4.73 (2d, 2 × 1H, J ) 11.6 Hz), 5.14
(brs, 1H), 5.85 (brd, 1H, J ) 10.3 Hz), 6.02 (brd, 1H, J ) 10.3
Hz), 7.24-7.39 (m, 10H); 13C NMR (50 MHz) δ 19.2, 71.6, 74.5,
76.7, 77.8, 126.6, 127.6, 128.1, 128.3, 128.3, 128.8, 128.9, 131.9,
138.6, 141.2. Anal. Calcd for C19H20O2: C, 81.40; H, 7.19.
Found: C, 81.17; H, 7.10.
(6-O-Ben zyl-4-O-m et h yl-2,3-d id eoxy-r-D-th r eo-h ex-2-
en op yr a n osyl)ben zen e (26): oil; Rf 0.59 (petroleum ether/
ethyl acetate, 2:1); [R]20D -173.6 (c 1.0, CH2Cl2); 1H NMR (300
MHz) δ 3.45 (s, 3H), 3.68 (dd, 1H, J ) 10.2, 7.0 Hz), 3.75 (dd,
1H, J ) 10.2, 5.4 Hz), 3.64-3.71 (m, 1H), 3.96 (ddd, 1H, J )
7.0, 5.4, 2.8 Hz), 4.49 and 4.56 (2d, 2 × 1H, J ) 11.9 Hz), 5.35
(brs, 1H), 6.23 (ddd, 1H, J ) 10.3, 2.8, 1.5 Hz), 6.32 (dd, 1H,
J ) 10.3, 2.8 Hz), 7.22-7.44 (m, 10H); 13C NMR (50 MHz) δ
56.8, 69.2, 70.2, 71.2, 73.3, 73.8, 114.9, 124.6, 126.4, 127.6,
127.7, 127.8, 128.5, 138.5, 139.3, 132.5. Anal. Calcd for
acetate, 5:1); [R]20 +47.3 (c 1.1, CH2Cl2); 1H NMR (300 MHz)
D
δ 2.31 (ddd, 1H, J ) 14.1, 7.6, 6.3 Hz), 2.49 (ddd, 1H, J )
14.1, 8.5, 5.9 Hz), 3.65 (dd, 1H, J ) 10.4, 3.4 Hz), 3.69 (dd,
1H, J ) 10.4, 4.3 Hz), 3.82 (ddd, 1H, J ) 7.9, 4.3, 3.4 Hz),
3.99 (dm, 1H, J ) 7.3 Hz), 4.25 (brdd, 1H, J ) 6.3, 5.9 Hz),
4.45 and 4.60 (2d, 2 × 1H, J ) 11.6 Hz), 4.52 and 4.62 (2d, 2
× 1H, J ) 12.2 Hz), 5.08 (dm, 1H, J ) 10.0 Hz), 5.10 (dm, 1H,
J ) 17.0 Hz), 5.84 (dm, 1H, J ) 10.4 Hz), 5.93 (dm, 1H, J )
10.4 hz), 5.79-5.95 (m, 1H), 7.20-7.50 (m, 10H); 13C NMR (50
MHz) δ 38.1, 69.3, 70.0, 71.1, 71.4, 72.2, 73.4, 117.4, 125.7,
127.6, 127.8, 127.9, 128.0, 128.4, 128.5, 131.2, 134.7, 138.3,
138.4. Anal. Calcd for C23H26O3: C, 78.83; H, 7.48. Found:
C, 78.75; H, 7.39.
C
20H22O3: C, 77.39; H, 7.14. Found: C, 78.07; H, 7.16.
Ackn owledgm en t. Financial support from the CNRS
and the MESR is gratefully acknowledged.
(4,6-Di-O-ben zyl-2,3-d id eoxy-r-D-er yth r o-h ex-2-en op y-
r a n osyl)eth ylen e (18a ): oil; Rf 0.40 (petroleum ether/ethyl
Su p p or t in g In for m a t ion Ava ila b le: 1H and 13C NMR
spectra for new compounds having microanalyses which do not
come within 0.45% for C calculated values (six compounds)
(24 pages). This material is contained in libraries on micro-
fiche, immediately follows this article in the microfilm version
of the journal, and can be ordered from the ACS; see any
current masthead page for ordering information.
acetate, 5:1); [R]20 +34.6 (c 0.9, CH2Cl2); 1H NMR (300 MHz)
D
δ 3.48-3.76 (m, 3H), 4.09 (dm, 1H, J ) 8.1 Hz), 4.45 and 4.60
(2d, 2 × 1H, J ) 11.5 Hz), 4.52 and 4.63 (2d, 2 × 1H, J ) 12.2
Hz), 4.73 (m, 1H), 5.24 (dm, 1H, J ) 10.3 Hz), 5.29 (dm, 1H,
J ) 17.3 Hz), 5.83 (ddd, 1H, J ) 10.4, 3.2, 1.7 Hz), 5.78-6.03
(m, 1H), 5.99 (ddd, 1H, J ) 10.4, 2.1, 2.1 Hz), 7.22-7.35 (m,
10H); 13C NMR (50 MHz) δ 69.3, 70.2, 70.9, 71.1, 73.3, 73.4,
117.4, 127.0, 127.7, 127.9, 128.0, 128.1, 128.5, 128.5, 129.3,
J O9714674